Comparing WHAM 6 and MINEQL+ 4.5 for the chemical speciation of Cu2+ in the rhizosphere of forest soils.

PubMed

Cloutier-Hurteau, Benoît; Sauvé, Sébastien; Courchesne, François

2007-12-01

Metal speciation data calculated by modeling could give useful information regarding the fate of metals in the rhizospheric environment. However, no comparative study has evaluated the relative accuracy of speciation models in this microenvironment. Consequently, the present study evaluates the reliability of free Cu ion (Cu2+) activity modeled by WHAM 6 and MINEQL+ 4.5 for 18 bulk and 18 rhizospheric soil samples collected in two Canadian forested areas located near industrial facilities. The modeling of Cu speciation was performed on water extracts using pH, dissolved organic carbon (DOC), major ions, and total dissolved Al, Ca, Cu, Mg, and Zn concentrations as input data. Four scenarios representing the composition of dissolved organic substances using fulvic, humic, and acetic acids were derived from the literature and used in the modeling exercise. Different scenarios were used to contrast soil components (rhizosphere vs bulk) and soil pH levels (acidic vs neutral to alkaline). Reference Cu2+ activity values measured by an ion-selective electrode varied between 0.39 and 41 nM. The model MINEQL+ 4.5 provided good predictions of Cu2+ activities [root-mean-square residual (RMSR)= 0.37], while predictions from WHAM 6 were poor (RMSR = 1.74) because they overestimated Cu complexation with DOC. Modeling with WHAM 6 could be improved by adjusting the proportion of inert DOC and the composition of DOC (RMSR = 0.94), but it remained weaker than predictions with MINEQL+ 4.5. These results suggested that the discrepancies between speciation models were attributed to differences in the binding capacity of humic substances with Cu, where WHAM 6 appeared to be too aggressive. Therefore, we concluded that chemical interactions occurring between Cu and DOC were key factors for an accurate simulation of Cu speciation, especially in rhizospheric forest soils, where high variation of the DOC concentration and composition are observed.

Effect of biochar amendment on compost organic matter composition following aerobic composting of manure.

PubMed

Hagemann, Nikolas; Subdiaga, Edisson; Orsetti, Silvia; de la Rosa, José María; Knicker, Heike; Schmidt, Hans-Peter; Kappler, Andreas; Behrens, Sebastian

2018-02-01

Biochar, a material defined as charred organic matter applied in agriculture, is suggested as a beneficial additive and bulking agent in composting. Biochar addition to the composting feedstock was shown to reduce greenhouse gas emissions and nutrient leaching during the composting process, and to result in a fertilizer and plant growth medium that is superior to non-amended composts. However, the impact of biochar on the quality and carbon speciation of the organic matter in bulk compost has so far not been the focus of systematic analyses, although these parameters are key to determine the long-term stability and carbon sequestration potential of biochar-amended composts in soil. In this study, we used different spectroscopic techniques to compare the organic carbon speciation of manure compost amended with three different biochars. A non-biochar-amended compost served as control. Based on Fourier-transformed infrared (FTIR) and 13 C nuclear magnetic resonance (NMR) spectroscopy we did not observe any differences in carbon speciation of the bulk compost independent of biochar type, despite a change in the FTIR absorbance ratio 2925cm -1 /1034cm -1 , that is suggested as an indicator for compost maturity. Specific UV absorbance (SUVA) and emission-excitation matrixes (EEM) revealed minor differences in the extractable carbon fractions, which only accounted for ~2-3% of total organic carbon. Increased total organic carbon content of biochar-amended composts was only due to the addition of biochar-C and not enhanced preservation of compost feedstock-C. Our results suggest that biochars do not alter the carbon speciation in compost organic matter under conditions optimized for aerobic decomposition of compost feedstock. Considering the effects of biochar on compost nutrient retention, mitigation of greenhouse gas emissions and carbon sequestration, biochar addition during aerobic composting of manure might be an attractive strategy to produce a sustainable, slow release fertilizer. Copyright © 2017 Elsevier B.V. All rights reserved.

Noninvasive Synchrotron-Based X-ray Raman Scattering Discriminates Carbonaceous Compounds in Ancient and Historical Materials [ In situ synchrotron-based X-Ray Raman scattering discriminates carbonaceous compounds in ancient and historical materials

DOE PAGES

Gueriau, Pierre; Rueff, Jean -Pascal; Bernard, Sylvain; ...

2017-09-13

Carbon compounds are ubiquitous and occur in a diversity of chemical forms in many systems including ancient and historic materials ranging from cultural heritage to paleontology. Determining their speciation cannot only provide unique information on their origin but may also elucidate degradation processes. Synchrotron-based X-ray absorption near-edge structure (XANES) spectroscopy at the carbon K-edge (280–350 eV) is a very powerful method to probe carbon speciation. However, the short penetration depth of soft X-rays imposes stringent constraints on sample type, preparation, and analytical environment. A hard X-ray probe such as X-ray Raman scattering (XRS) can overcome many of these difficulties. Heremore » we report the use of XRS at ~6 keV incident energy to collect carbon K-edge XANES data and probe the speciation of organic carbon in several specimens relevant to cultural heritage and natural history. This methodology enables the measurement to be done in a nondestructive way, in air, and provides information that is not compromised by surface contamination by ensuring that the dominant signal contribution is from the bulk of the probed material. Using the backscattering geometry at large photon momentum transfer maximizes the XRS signal at the given X-ray energy and enhances nondipole contributions compared to conventional XANES, thereby augmenting the speciation sensitivity. The capabilities and limitations of the technique are discussed. As a result, we show that despite its small cross section, for a range of systems the XRS method can provide satisfactory signals at realistic experimental conditions. XRS constitutes a powerful complement to FT-IR, Raman, and conventional XANES spectroscopy, overcoming some of the limitations of these techniques.« less

Speciation and Release Kinetics of Cadmium in an Alkaline Paddy Soil Under Various Flooding Periods and Draining Conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

S Khaokaew; R Chaney; G Landrot

2011-12-31

This study determined Cd speciation and release kinetics in a Cd-Zn cocontaminated alkaline paddy soil, under various flooding periods and draining conditions, by employing synchrotron-based techniques, and a stirred-flow kinetic method. Results revealed that varying flooding periods and draining conditions affected Cd speciation and its release kinetics. Linear least-squares fitting (LLSF) of bulk X-ray absorption fine structure (XAFS) spectra of the air-dried, and the 1 day-flooded soil samples, showed that at least 50% of Cd was bound to humic acid. Cadmium carbonates were found as the major species at most flooding periods, while a small amount of cadmium sulfide wasmore » found after the soils were flooded for longer periods. Under all flooding and draining conditions, at least 14 mg/kg Cd was desorbed from the soil after a 2-hour desorption experiment. The results obtained by micro X-ray fluorescence ({mu}-XRF) spectroscopy showed that Cd was less associated with Zn than Ca, in most soil samples. Therefore, it is more likely that Cd and Ca will be present in the same mineral phases rather than Cd and Zn, although the source of these two latter elements may originate from the same surrounding Zn mines in the Mae Sot district.« less

Innovative methods in soil phosphorus research: A review

PubMed Central

Kruse, Jens; Abraham, Marion; Amelung, Wulf; Baum, Christel; Bol, Roland; Kühn, Oliver; Lewandowski, Hans; Niederberger, Jörg; Oelmann, Yvonne; Rüger, Christopher; Santner, Jakob; Siebers, Meike; Siebers, Nina; Spohn, Marie; Vestergren, Johan; Vogts, Angela; Leinweber, Peter

2015-01-01

Phosphorus (P) is an indispensable element for all life on Earth and, during the past decade, concerns about the future of its global supply have stimulated much research on soil P and method development. This review provides an overview of advanced state-of-the-art methods currently used in soil P research. These involve bulk and spatially resolved spectroscopic and spectrometric P speciation methods (1 and 2D NMR, IR, Raman, Q-TOF MS/MS, high resolution-MS, NanoSIMS, XRF, XPS, (µ)XAS) as well as methods for assessing soil P reactions (sorption isotherms, quantum-chemical modeling, microbial biomass P, enzymes activity, DGT, 33P isotopic exchange, 18O isotope ratios). Required experimental set-ups and the potentials and limitations of individual methods present a guide for the selection of most suitable methods or combinations. PMID:26167132

Nickel speciation in several serpentine (ultramafic) topsoils via bulk synchrotron-based techniques

USDA-ARS?s Scientific Manuscript database

Serpentine soils are extensively studied because of their unique soil chemical properties and flora. They commonly have high magnesium-to-calcium ratios and elevated concentrations of trace metals including nickel, cobalt, and chromium. Several nickel hyperaccumulator plants are native to serpenti...

Speciation and Localization of Arsenic in White and Brown Rice Grains

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meharg, Andrew A.; Lombi, Enzo; Williams, Paul N.

2008-06-30

Synchrotron-based X-ray fluorescence (S-XRF) was utilized to locate arsenic (As) in polished (white) and unpolished (brown) rice grains from the United States, China, and Bangladesh. In white rice As was generally dispersed throughout the grain, the bulk of which constitutes the endosperm. In brown rice As was found to be preferentially localized at the surface, in the region corresponding to the pericarp and aleurone layer. Copper, iron, manganese, and zinc localization followed that of arsenic in brown rice, while the location for cadmium and nickel was distinctly different, showing relatively even distribution throughout the endosperm. The localization of As inmore » the outer grain of brown rice was confirmed by laser ablation ICP?MS. Arsenic speciation of all grains using spatially resolved X-ray absorption near edge structure (?-XANES) and bulk extraction followed by anion exchange HPLC?ICP?MS revealed the presence of mainly inorganic As and dimethylarsinic acid (DMA). However, the two techniques indicated different proportions of inorganic:organic As species. A wider survey of whole grain speciation of white (n = 39) and brown (n = 45) rice samples from numerous sources (field collected, supermarket survey, and pot trials) showed that brown rice had a higher proportion of inorganic arsenic present than white rice. Furthermore, the percentage of DMA present in the grain increased along with total grain arsenic.« less

Speciation And Localization Of Arsenic In White And Brown Rice Grains

EPA Science Inventory

Synchrotron-based X-ray fluorescence (S-XRF) was utilized to locate arsenic (As) in polished (white) and unpolished (brown) rice grains from the United States, China, and Bangladesh. In white rice As was generally dispersed throughout the grain, the bulk of which constitutes the...

Spatial and Temporal Variability in Sediment P Distribution and Speciation in Coastal Louisiana

NASA Astrophysics Data System (ADS)

Bowes, K.; White, J. R.; Maiti, K.

2017-12-01

Excess loading of phosphorus (P) and nitrogen (N) into aquatic systems leads to degradation of water quality and diminished important ecosystem services. In the Northern Gulf of Mexico (NGOM), excess P and N loading has led to a seasonally present hypoxic area with less than 2 mg/L O2 in bottom waters, approximating 26,000 km2 in 2017. A sequential extraction (SEDEX) method was performed on surficial sediments from five different coastal and shelf sites as a function of distance from the Mississippi River mouth in the NGOM. To better quantify temporal variability in P distribution and speciation, samples were collected during both low (August) and high (May) river flow regimes. Sequential extraction techniques have been successful in separating pools of P into exchangeable or loosely sorbed P, Fe-P, Authigenic-P, Detrital-P, and Organic-P. Preliminary results suggest Authigenic-P is approximately 3-6 times more concentrated in NGOM sediments than all other P pools. Fractionation results did not show a consistent trend with sediment depth. Sediment samples had an average moisture content of 58.72% ± 12.06% and an average bulk density of 0.582 ± 0.275 g/cm3. Continued analysis of P speciation and cycling in NGOM sediments is critical in understanding the driving force behind coastal eutrophication and informing effective nutrient management strategies.

Speciation and distribution of arsenic and localization of nutrients in rice grains

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lombi, E.; Scheckel, K.G.; Pallon, J.

2012-09-05

Arsenic (As) contamination of rice grains and the generally low concentration of micronutrients in rice have been recognized as a major concern for human health. Here, we investigated the speciation and localization of As and the distribution of (micro)nutrients in rice grains because these are key factors controlling bioavailability of nutrients and contaminants. Bulk total and speciation analyses using high-pressure liquid chromatography (HPLC)-inductively coupled plasma mass spectrometry (ICP-MS) and X-ray absorption near-edge spectroscopy (XANES) was complemented by spatially resolved microspectroscopic techniques ({mu}-XANES, {mu}-X-ray fluorescence ({mu}-XRF) and particle induced X-ray emission (PIXE)) to investigate both speciation and distribution of As andmore » localization of nutrients in situ. The distribution of As and micronutrients varied between the various parts of the grains (husk, bran and endosperm) and was characterized by element-specific distribution patterns. The speciation of As in bran and endosperm was dominated by As(III)-thiol complexes. The results indicate that the translocation from the maternal to filial tissues may be a bottleneck for As accumulation in the grain. Strong similarities between the distribution of iron (Fe), manganese (Mn) and phosphorus (P) and between zinc (Zn) and sulphur (S) may be indicative of complexation mechanisms in rice grains.« less

Combining Textural Techniques to Explore Effects of Diagenesis and Low-grade Metamorphism on Iron Mineralogy and Iron Speciation

NASA Astrophysics Data System (ADS)

Slotznick, S. P.; Webb, S.; Eiler, J. M.; Kirschvink, J. L.; Fischer, W. W.

2016-12-01

Iron chemistry and mineralogy in the sedimentary rocks provide a valuable tool for studying paleoenvironmental conditions due to the fact that iron atoms can take on either the +II or +III valence state under geological redox conditions. One method utilizing this redox chemistry is `iron speciation', a bulk chemical sequential extraction technique that maps proportions of iron species to redox conditions empirically calibrated from modern sediments. However, all Precambrian and many Phanerozoic rocks have experienced post-depositional processes; it is vital to explore their effects on iron mineralogy and speciation. We combined light and electron microscopy, magnetic microscopy, (synchrotron-based) microprobe x-ray spectroscopy, and rock magnetic measurements in order to deconvolve secondary overprints from primary phases and provide quantitative measurement of iron minerals. These techniques were applied to excellently-preserved shale and siltstone samples of the 1.4 Ga lower Belt Supergroup, Montana and Idaho, USA, spanning a metamorphic gradient from sub-biotite to garnet zone. Previously measured Silurian-Devonian shales, sandstones, and carbonates in Maine and Vermont, USA spanning from the chlorite to kyanite zone provided additional well-constrained, quantitative data for comparison and to extend our analysis. In all of the studied samples, pyrrhotite formation occurred at the sub-biotite or sub-chlorite zone. Pyrrhotite was interpreted to form from pyrite and/or other iron phases based on lithology; these reactions can affect the paleoredox proxy. Iron carbonates can also severely influence iron speciation results since they often form in anoxic pore fluids during diagenesis; textural analyses of the Belt Supergroup samples highlighted that iron-bearing carbonates were early diagenetic cements or later diagenetic overprints. The inclusion of iron from diagenetic minerals during iron speciation analyses will skew results by providing a view of pore-fluid redox, not ancient water column chemistry. While our analyses and biological indicators suggest that the studied samples of the lower Belt Supergroup and New England were deposited in oxic water columns, iron speciation results imply anoxic/ferruginous conditions due to diagenetic alterations affecting the record.

Approach of the Molten Salt Chemistry for Aluminium Production: High Temperature NMR Measurements, Molecular Dynamics and DFT Calculations

NASA Astrophysics Data System (ADS)

Machado, Kelly; Zanghi, Didier; Sarou-Kanian, Vincent; Cadars, Sylvian; Burbano, Mario; Salanne, Mathieu; Bessada, Catherine

In aluminum production, the electrolyte is a molten fluorides mixture typically around 1000°C. In order to have a better understanding of the industrial process, it is necessary to have a model which will describe the molten salts on a wide range of compositions and temperatures, to accurately cover all the combinations that may be encountered in an operating electrolysis vessel. The aim of this study is to describe the speciation in the electrolyte in terms of anionic species in the bulk materials far from electrodes. To determine the speciation in situ at high temperature in the absence of an electrical field, we develop an original approach combining experimental methods such as Nuclear Magnetic Resonance spectroscopy (NMR) at high temperature with Molecular Dynamics (MD) simulation coupled with first principle calculations based on Density Functional Theory (DFT). This approach allows the calculation of NMR parameters and the comparison with the experimental ones. It will be provide an additional validation and constraint of the model used for MD. We test this approach on the model NaF-AlF3 system.

MOVES2014: Fuel Effects, Toxics Emissions, Total Organic Gases (TOG) and PM Speciation Analysis

EPA Science Inventory

The report updates fuel effects applied in MOVES2013 for selected fuel content and bulk fuel properties in gasolines containing up to 20% ethanol for gasoline fuel sulfur content and for fuel ethanol content for E85 and similar blends. These adjustments are applied to vehicle exh...

Nickel speciation in several serpentine (ultramafic) topsoils via bulk synchrotron-based techniques

DOE Office of Scientific and Technical Information (OSTI.GOV)

Siebecker, Matthew G.; Chaney, Rufus L.; Sparks, Donald L.

2017-07-01

Serpentine soils have elevated concentrations of trace metals including nickel, cobalt, and chromium compared to non-serpentine soils. Identifying the nickel bearing minerals allows for prediction of potential mobility of nickel. Synchrotron-based techniques can identify the solid-phase chemical forms of nickel with minimal sample treatment. Element concentrations are known to vary among soil particle sizes in serpentine soils. Sonication is a useful method to physically disperse sand, silt and clay particles in soils. Synchrotron-based techniques and sonication were employed to identify nickel species in discrete particle size fractions in several serpentine (ultramafic) topsoils to better understand solid-phase nickel geochemistry. Nickel commonlymore » resided in primary serpentine parent material such as layered-phyllosilicate and chain-inosilicate minerals and was associated with iron oxides. In the clay fractions, nickel was associated with iron oxides and primary serpentine minerals, such as lizardite. Linear combination fitting (LCF) was used to characterize nickel species. Total metal concentration did not correlate with nickel speciation and is not an indicator of the major nickel species in the soil. Differences in soil texture were related to different nickel speciation for several particle size fractionated samples. A discussion on LCF illustrates the importance of choosing standards based not only on statistical methods such as Target Transformation but also on sample mineralogy and particle size. Results from the F-test (Hamilton test), which is an underutilized tool in the literature for LCF in soils, highlight its usefulness to determine the appropriate number of standards to for LCF. EXAFS shell fitting illustrates that destructive interference commonly found for light and heavy elements in layered double hydroxides and in phyllosilicates also can occur in inosilicate minerals, causing similar structural features and leading to false positive results in LCF.« less

How Does Boiling in the Earth's Crust Influence Metal Speciation and Transport?

NASA Astrophysics Data System (ADS)

Kam, K.; Lemke, K.

2014-12-01

The presence of large quantities of precious metals, such as gold and copper, near the Earth's surface (upper crust) is commonly attributed to transport in aqueous solution and precipitation upon variations in temperature and pressure. As a consequence, gold exploration is closely linked to solution chemistry, i.e. hydrothermal processes involving aqueous fluids with densities of around unity. However, as crustal fluids buoyantly ascend, boiling produces a coexisting low-density aqueous liquid with fundamentally different physical and chemical properties, and a, most importantly, a high affinity for coinage metals (Heinrich et al., Econ Geol., 1992, 87, 1566). From recent experimental studies of Au (Hurtig and Williams-Jones, 2014, Geochim. Cosmochim. Acta,, 127, 304), we know that metal speciation in this low-density phase differs fundamentally from that observed in bulk solution, clearly, with important implications for Au, and metal speciation in general, transport and ore concentrations processes (these processes would also be operable in industrial geothermal plants given the quite special solvent properties of steam). In brief, this study focuses on the speciation of select metal halides in bulk solution as well as in water vapor, and is driven by our need to understand the solvent properties of around 2.0x109 cubic kilometers of free water (or 2,500 times as much water as stored in all lakes and rivers) present in the Earth's crust. The scope of this study has particular applications in the geothermal and oil industries, as both deal with high temperature low-density aqueous fluids. Understanding how metal halide species behave upon boiling can also provide insight into how metals, such as copper and silver, coat turbine equipment and steam piping in geothermal plants, ultimately rendering these components inoperable. This study will also provide preliminary results from mass spectrometric experiments of transition metal halides, and will be augmented with results from molecular simulations of metal halides that are aimed at characterizing the nature (i.e. relativistic structures and energies) of metal clusters in water vapor.

A novel von Hamos spectrometer for efficient X-ray emission spectroscopy in the laboratory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anklamm, Lars, E-mail: anklamm@physik.tu-berlin.de; Schlesiger, Christopher; Malzer, Wolfgang

2014-05-15

We present a novel, highly efficient von Hamos spectrometer for X-ray emission spectroscopy (XES) in the laboratory using highly annealed pyrolitic graphite crystals as the dispersive element. The spectrometer covers an energy range from 2.5 keV to 15 keV giving access to chemical speciation and information about the electronic configuration of 3d transition metals by means of the Kβ multiplet. XES spectra of Ti compounds are presented to demonstrate the speciation capabilities of the instrument. A spectral resolving power of E/ΔE = 2000 at 8 keV was achieved. Typical acquisition times range from 10 min for bulk material to hours formore » thin samples below 1 μm.« less

Speciated Elemental and Isotopic Characterization of Atmospheric Aerosols - Recent Advances

NASA Astrophysics Data System (ADS)

Shafer, M.; Majestic, B.; Schauer, J.

2007-12-01

Detailed elemental, isotopic, and chemical speciation analysis of aerosol particulate matter (PM) can provide valuable information on PM sources, atmospheric processing, and climate forcing. Certain PM sources may best be resolved using trace metal signatures, and elemental and isotopic fingerprints can supplement and enhance molecular maker analysis of PM for source apportionment modeling. In the search for toxicologically relevant components of PM, health studies are increasingly demanding more comprehensive characterization schemes. It is also clear that total metal analysis is at best a poor surrogate for the bioavailable component, and analytical techniques that address the labile component or specific chemical species are needed. Recent sampling and analytical developments advanced by the project team have facilitated comprehensive characterization of even very small masses of atmospheric PM. Historically; this level of detail was rarely achieved due to limitations in analytical sensitivity and a lack of awareness concerning the potential for contamination. These advances have enabled the coupling of advanced chemical characterization to vital field sampling approaches that typically supply only very limited PM mass; e.g. (1) particle size-resolved sampling; (2) personal sampler collections; and (3) fine temporal scale sampling. The analytical tools that our research group is applying include: (1) sector field (high-resolution-HR) ICP-MS, (2) liquid waveguide long-path spectrophotometry (LWG-LPS), and (3) synchrotron x-ray absorption spectroscopy (sXAS). When coupled with an efficient and validated solubilization method, the HR-ICP-MS can provide quantitative elemental information on over 50 elements in microgram quantities of PM. The high mass resolution and enhanced signal-to-noise of HR-ICP-MS significantly advance data quality and quantity over that possible with traditional quadrupole ICP-MS. The LWG-LPS system enables an assessment of the soluble/labile components of PM, while simultaneously providing critical oxidation state speciation data. Importantly, the LWG- LPS can be deployed in a semi-real-time configuration to probe fine temporal scale variations in atmospheric processing or sources of PM. The sXAS is providing complementary oxidation state speciation of bulk PM. Using examples from our research; we will illustrate the capabilities and applications of these new methods.

Influence of soil pH on the sorption of ionizable chemicals: modeling advances.

PubMed

Franco, Antonio; Fu, Wenjing; Trapp, Stefan

2009-03-01

The soil-water distribution coefficient of ionizable chemicals (K(d)) depends on the soil acidity, mainly because the pH governs speciation. Using pH-specific K(d) values normalized to organic carbon (K(OC)) from the literature, a method was developed to estimate the K(OC) of monovalent organic acids and bases. The regression considers pH-dependent speciation and species-specific partition coefficients, calculated from the dissociation constant (pK(a)) and the octanol-water partition coefficient of the neutral molecule (log P(n)). Probably because of the lower pH near the organic colloid-water interface, the optimal pH to model dissociation was lower than the bulk soil pH. The knowledge of the soil pH allows calculation of the fractions of neutral and ionic molecules in the system, thus improving the existing regression for acids. The same approach was not successful with bases, for which the impact of pH on the total sorption is contrasting. In fact, the shortcomings of the model assumptions affect the predictive power for acids and for bases differently. We evaluated accuracy and limitations of the regressions for their use in the environmental fate assessment of ionizable chemicals.

Investigation of arsenic species in tailings and windblown dust from a gold mining area.

PubMed

Ono, F B; Tappero, R; Sparks, D; Guilherme, L R G

2016-01-01

Research has shown the presence of high levels of arsenic (up to 2666 mg As kg(-1)) in tailings from a gold mining area of Brazil. This is an important point of attention, generating concerns about impacts on human health. Yet, a recent study showed that As bioaccessibility in the same area was very low (<4.4%). Thus, determination of the direct solid-phase speciation of As in the mine tailings and windblown dust is needed to explain this low bioaccessibility. Mine samples were collected from four subareas and windblown dust from eight sites. Synchrotron-based bulk-X-ray absorption near-edge structure (bulk-XANES) spectroscopy, micro-X-ray absorption near-edge structure (μ-XANES), and μ-X-ray fluorescence (μ-SXRF) spectroscopy were applied to determine As speciation. Bulk-XANES spectra indicated that As occurs as the As(V) oxidation state. Micro-XANES and μ-SXRF analyses revealed that As was also present as arsenopyrite (FeAsS) and its weathering products, but mostly it was As(V) as poorly crystalline ferric arsenate. This supports the findings of low bioaccessible As and highlights the importance of Fe oxides in immobilizing As in the terrestrial environment. All air particulate samples exhibited As-rich particles (up to 313 mg As kg(-1)). The air particulates exhibited solid-phase As species very similar to those found in the mine samples, which indicates that As in the windblown dust is not easily available.

AS SPECIATION AND EFFECTS OF PH AND PHOSPHATE ON THE MOBILIZATION OF AS IN SOILS FROM A LEAD SMELTING SITE. PUBLISHED IN ADVANCED PHOTON SOURCE ACTIVITY REPORT 2003.

EPA Science Inventory

Arsenic in soils from the Asarco lead smelter in East Helena, Montana was characterized by X-ray absorption spectroscopy (XAS). Arsenic oxidation state and mineralogy were analyzed as a function of depth and surface distribution using bulk and microprobe XAS. These results were c...

Speciation at the Mogollon Rim in the Arizona Mountain Kingsnake (Lampropeltis pyromelana).

PubMed

Burbrink, Frank T; Yao, Helen; Ingrasci, Matthew; Bryson, Robert W; Guiher, Timothy J; Ruane, Sara

2011-09-01

Studies of speciation and taxon delimitation are usually decoupled. Combining these methods provides a stronger theoretical ground for recognizing new taxa and understanding processes of speciation. Using coalescent methods, we examine speciation, post-speciation population demographics, and taxon delimitation in the Arizona Mountain Kingsnake (Lampropeltis pyromelana), a species restricted to high elevations in southwestern United States and northern Mexico (SW). These methods provide a solid foundation for understanding how biogeographic barriers operate at the regional scale in the SW. Bayesian species delimitation methods, using three loci from samples of L. pyromelana taken throughout their range, show strong support for the existence of two species that are separated by low elevation habitats found between the Colorado Plateau/ Mogollon Rim and the Sierra Madre Occidental. Our results suggest an allopatric mode of speciation given the near absence of gene flow over time, which resulted in two lineages of unequal population sizes. Speciation likely occurred prior to the Pleistocene, during the aridification of the SW and/or the uplift of the Colorado Plateau, and while these species occupy similar high-elevation niches, they are isolated by xeric conditions found in the intervening low deserts. Furthermore, post-speciation demographics suggest that populations of both lineages were not negatively impacted by climate change throughout the Pleistocene. Finally, our results suggest that at least for this group, where divergence is old and gene flow is low, Bayesian species delimitation performs well. Copyright © 2011 Elsevier Inc. All rights reserved.

Self-consistent approach for neutral community models with speciation

NASA Astrophysics Data System (ADS)

Haegeman, Bart; Etienne, Rampal S.

2010-03-01

Hubbell’s neutral model provides a rich theoretical framework to study ecological communities. By incorporating both ecological and evolutionary time scales, it allows us to investigate how communities are shaped by speciation processes. The speciation model in the basic neutral model is particularly simple, describing speciation as a point-mutation event in a birth of a single individual. The stationary species abundance distribution of the basic model, which can be solved exactly, fits empirical data of distributions of species’ abundances surprisingly well. More realistic speciation models have been proposed such as the random-fission model in which new species appear by splitting up existing species. However, no analytical solution is available for these models, impeding quantitative comparison with data. Here, we present a self-consistent approximation method for neutral community models with various speciation modes, including random fission. We derive explicit formulas for the stationary species abundance distribution, which agree very well with simulations. We expect that our approximation method will be useful to study other speciation processes in neutral community models as well.

Speciation of arsenic, selenium, and chromium in wildfire impacted soils and ashes

USGS Publications Warehouse

Wolf, Ruth E.; Hoefen, Todd M.; Hageman, Philip L.; Morman, Suzette A.; Plumlee, Geoffrey S.

2010-01-01

In 2007-09, California experienced several large wildfires that damaged large areas of forest and destroyed many homes and buildings. The U.S. Geological Survey collected samples from the Harris, Witch, Grass Valley, Ammo, Santiago, Canyon, Jesusita, and Station fires for testing to identify any possible characteristics of the ashes and soils from burned areas that may be of concern for their impact on water quality, human health, and endangered species. The samples were subjected to analysis for bulk chemical composition for 44 elements by inductively coupled plasma mass spectrometry (ICP-MS) after acid digestion and de-ionized water leach tests for pH, alkalinity, conductivity, and anions. Water leach tests generated solutions ranging from pH 10-12, suggesting that ashes can generate caustic alkalinity in contact with rainwater or body fluids (for example, sweat and fluids in the respiratory tract). Samples from burned residential areas in the 2007 fires had elevated levels for several metals, including: As, Pb, Sb, Cu, Zn, and Cr. In some cases, the levels found were above the U.S. Environmental Protection Agency (USEPA) preliminary remediation goals (PRG) for soils. Speciation analyses were conducted on de-ionized water and simulated lung fluid leachates for As(III), As(V), Se(IV), Se(VI), Cr(III), and Cr(VI). All species were determined in the same analytical run using an ion-pairing HPLC-ICP-MS method. For leachates containing high levels of total Cr, the majority of the chromium was present in the hexavalent, Cr(VI), form. Higher total and hexavalent chromium levels were observed for samples collected from burned residential areas. Arsenic was also generally present in the more oxidized, As(V), form. Selenium (IV) and (VI) were present, but typically at levels below 2 ppb for most samples. Stability studies of leachate solutions under different storage conditions were performed and the suitability of different sample preservation methods for speciation analysis will be discussed.

Selenium analysis in waters. Part 2: Speciation methods.

PubMed

LeBlanc, Kelly L; Kumkrong, Paramee; Mercier, Patrick H J; Mester, Zoltán

2018-06-21

In aquatic ecosystems, there is often no correlation between the total concentration of selenium present in the water column and the toxic effects observed in that environment. This is due, in part, to the variation in the bioavailability of different selenium species to organisms at the base of the aquatic food chain. The first part of this review (Kumkrong et al., 2018) discusses regulatory framework and standard methodologies for selenium analysis in waters. In this second article, we are reviewing the state of speciation analysis and importance of speciation data for decision makers in industry and regulators. We look in detail at fractionation methods for speciation, including the popular selective sequential hydride generation. We examine advantages and limitations of these methods, in terms of achievable detection limits and interferences from other matrix species, as well as the potential to over- or under-estimate operationally-defined fractions based on the various conversion steps involved in fractionation processes. Additionally, we discuss methods of discrete speciation (through separation methods), their importance in analyzing individual selenium species, difficulties associated with their implementation, as well as ways to overcome these difficulties. We also provide a brief overview of biological treatment methods for the remediation of selenium-contaminated waters. We discuss the importance of selenium speciation in the application of these methods and their potential to actually increase the bioavailability of selenium despite decreasing its total waterborne concentration. Copyright © 2018. Published by Elsevier B.V.

Fate of Zinc Oxide Nanoparticles Coated onto Macronutrient Fertilizers in an Alkaline Calcareous Soil

PubMed Central

Milani, Narges; Hettiarachchi, Ganga M.; Kirby, Jason K.; Beak, Douglas G.; Stacey, Samuel P.; McLaughlin, Mike J.

2015-01-01

Zinc oxide (ZnO) nanoparticles may provide a more soluble and plant available source of Zn in Zn fertilizers due to their greater reactivity compared to equivalent micron- or millimetre-sized (bulk) particles. However, the effect of soil on solubility, spatial distribution and speciation of ZnO nanoparticles has not yet been investigated. In this study, we examined the diffusion and solid phase speciation of Zn in an alkaline calcareous soil following application of nanoparticulate and bulk ZnO coated fertilizer products (monoammonium phosphate (MAP) and urea) using laboratory-based x-ray techniques and synchrotron-based μ-x-ray fluorescence (μ–XRF) mapping and absorption fine structure spectroscopy (μ–XAFS). Mapping of the soil-fertilizer reaction zones revealed that most of the applied Zn for all treatments remained on the coated fertilizer granule or close to the point of application after five weeks of incubation in soil. Zinc precipitated mainly as scholzite (CaZn2(PO4)2.2H2O) and zinc ammonium phosphate (Zn(NH4)PO4) species at the surface of MAP granules. These reactions reduced dissolution and diffusion of Zn from the MAP granules. Although Zn remained as zincite (ZnO) at the surface of urea granules, limited diffusion of Zn from ZnO-coated urea granules was also observed for both bulk and nanoparticulate ZnO treatments. This might be due to either the high pH of urea granules, which reduced solubility of Zn, or aggregation (due to high ionic strength) of released ZnO nanoparticles around the granule/point of application. The relative proportion of Zn(OH)2 and ZnCO3 species increased for all Zn treatments with increasing distance from coated MAP and urea granules in the calcareous soil. When coated on macronutrient fertilizers, Zn from ZnO nanoparticles (without surface modifiers) was not more mobile or diffusible compared to bulk forms of ZnO. The results also suggest that risk associated with the presence of ZnO NPs in calcareous soils would be the same as bulk sources of ZnO. PMID:25965385

Speciation of Soil Phosphorus Assessed by XANES Spectroscopy at Different Spatial Scales

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hesterberg, Dean; McNulty, Ian; Thieme, Juergen

Precise management of soil phosphorus (P) to meet competing demands of agriculture and environmental protection can benefit from more comprehensive characterization of P speciation in soils. Our objectives were to provide spatial context for spectroscopic analyses of soil P speciation in relation to molecular-scale species and landscape-scale management of P, and to compare soil P-species diversity from spectroscopic measurements at submicron and millimeter scales. The spatial range of ~26 orders of magnitude between atomic and field scales presents a challenge to upscaling and downscaling information from spectroscopic analyses of soils. Scanning fluorescence X-ray microscopy images of a 50-mm ´ 45-mmmore » area of an organic soil sample showed heterogeneous distributions of P, Al, and Si. Microscale X-ray absorption near edge structure (μ-XANES) spectra collected at the P K-edge from 12 spots on the soil sample exhibited diverse features that indicated variations in highly localized P speciation. Linear combination fitting analysis of the μ-XANES spectra included various proportions of three standards that appeared in fits for most spots and five standards that appeared in fits for one spot each. The fit to a bulk-soil spectrum was dominated by two of the common standards in the μ-XANES fits, and a fit to the sum of m-XANES spectra included four of the standards. Lastly, these results illustrate a gain in P species sensitivity from spatially resolved XANES analysis. Integrating spectroscopic analyses from multiple scales determines soil P species diversity and will ultimately help connect speciation to the chemical reactivity and mobility of P in soils.« less

Speciation of Soil Phosphorus Assessed by XANES Spectroscopy at Different Spatial Scales

DOE PAGES

Hesterberg, Dean; McNulty, Ian; Thieme, Juergen

2017-07-27

Precise management of soil phosphorus (P) to meet competing demands of agriculture and environmental protection can benefit from more comprehensive characterization of P speciation in soils. Our objectives were to provide spatial context for spectroscopic analyses of soil P speciation in relation to molecular-scale species and landscape-scale management of P, and to compare soil P-species diversity from spectroscopic measurements at submicron and millimeter scales. The spatial range of ~26 orders of magnitude between atomic and field scales presents a challenge to upscaling and downscaling information from spectroscopic analyses of soils. Scanning fluorescence X-ray microscopy images of a 50-mm ´ 45-mmmore » area of an organic soil sample showed heterogeneous distributions of P, Al, and Si. Microscale X-ray absorption near edge structure (μ-XANES) spectra collected at the P K-edge from 12 spots on the soil sample exhibited diverse features that indicated variations in highly localized P speciation. Linear combination fitting analysis of the μ-XANES spectra included various proportions of three standards that appeared in fits for most spots and five standards that appeared in fits for one spot each. The fit to a bulk-soil spectrum was dominated by two of the common standards in the μ-XANES fits, and a fit to the sum of m-XANES spectra included four of the standards. Lastly, these results illustrate a gain in P species sensitivity from spatially resolved XANES analysis. Integrating spectroscopic analyses from multiple scales determines soil P species diversity and will ultimately help connect speciation to the chemical reactivity and mobility of P in soils.« less

Invisible and microscopic gold in pyrite: Methods and new data for massive sulfide ores of the Urals

NASA Astrophysics Data System (ADS)

Vikentyev, I. V.

2015-07-01

Au speciation in sulfides (including "invisible" Au), which mostly controls the loss of Au during ore dressing, is discussed. Modern methods of analysis of Au speciation, with discussion of limitations by locality and sensitivity, are reviewed. The results of sulfide investigation by the methods of scanning and transmission electron microscopy, mass spectrometric analysis with laser ablation (LA-ICP-MS), the thermochemical method (study of ionic Au speciation), and automated "quantitative mineralogy," are demonstrated for weakly metamorphosed VHMS deposits of the Urals (Galkinsk and Uchaly). Significant content of Au is scattered in sulfides, such as pyrite, chalcopyrite, and sphalerite, with quantitative predomination of pyrite. The portion of such "invisible" gold ranges from <10% (Galkinsk deposit) to 85% (Uchaly deposit). Major part of "invisible" gold occurs as micron- to nanoscale particles of Au minerals. The portion of gold structurally bound in pyrite lattice (from the bulk concentration of Au in pyrite) is estimated to be from few % (the Galkinsk deposit) to 20-25% (the Uchaly deposit). The presence of As and Sb in pyrite and sphalerite, as well as other trace elements (Te, Co, Mn, Cu, Hg, and Ag in both as well as Fe in sphalerite) stimulates the incorporation of Au in sulfide, but mostly in defect-associated, not isomorphic form. Micron particles of Ag sulfosalts (pyrargyrite, freibergite, stephanite, polybasite, pyrostilpnite, argentotetrahedrite, pearceite, proustite), Au-Ag alloys (from gold of high fineness to küstelite), Ag and Au-Ag tellurides (hessite, empressite, calaverite), and occasional Au-Ag sulfides (petrovskaite, uytenbogaardtite) were registered in the areas of Au enrichment of both deposits; selenotelluride (kurilite) particles were found on the Galkinsk deposit. Nanoscale (1-50 nm) native gold (spherical and disk-shaped particles, flakes) with a monocrystal diffraction pattern of some particles and a ring diffraction pattern of other particles was registered in the ores of these deposits by the methods of transmission electron microscopy. The low degree (or absence) of metamorphic recrystallization results in (1) predomination of thin intergrowths of sulfides, which is the main reason for the bad concentration of ores (especially for the Galkinsk deposit) and (2) the high portion of "invisible" gold in the massive sulfide ores, which explains the low yield of Au in copper and zinc concentrates, since it is lost in tailings with predominating pyrite.

The Interplay of Al and Mg Speciation in Advanced Mg Battery Electrolyte Solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

See, Kimberly A.; Chapman, Karena W.; Zhu, Lingyang

2016-01-13

Mg batteries are an attractive alternative to Li-based energy storage due to the possibility of higher volumetric capacities with the added advantage of using sustainable materials. A promising emerging electrolyte for Mg batteries is the magnesium aluminum chloride complex (MACC) which shows high Mg electrodeposition and stripping efficiencies and relatively high anodic stabilities. As prepared, MACC is inactive with respect to Mg deposition; however, efficient Mg electrodeposition can be achieved following an electrolytic conditioning process. Through the use of Raman spectroscopy, surface enhanced Raman spectroscopy, 27Al and 35Cl nuclear magnetic resonance spectroscopy, and pair distribution function analysis, we explore themore » active vs inactive complexes in the MACC electrolyte and demonstrate the codependence of Al and Mg speciation. These techniques report on significant changes occurring in the bulk speciation of the conditioned electrolyte relative to the as-prepared solution. Analysis shows that the active Mg complex in conditioned MACC is very likely the [Mg2(μ–Cl)3·6THF]+ complex that is observed in the solid state structure. Additionally, conditioning creates free Cl– in the electrolyte solution, and we suggest the free Cl– adsorbs at the electrode surface to enhance Mg electrodeposition.« less

THE ONTARIO HYDRO METHOD FOR SPECIATED MERCURY MEASUREMENTS: ISSUES AND CONSIDERATIONS

EPA Science Inventory

The Ontario Hydro (OH) method has been developed for the measurement of total and speciated mercury emissions from coal-fired combustion sources. The OH method was initially developed to support EPA's information collection request to characterize and inventory mercury emissions ...

New analytic results for speciation times in neutral models.

PubMed

Gernhard, Tanja

2008-05-01

In this paper, we investigate the standard Yule model, and a recently studied model of speciation and extinction, the "critical branching process." We develop an analytic way-as opposed to the common simulation approach-for calculating the speciation times in a reconstructed phylogenetic tree. Simple expressions for the density and the moments of the speciation times are obtained. Methods for dating a speciation event become valuable, if for the reconstructed phylogenetic trees, no time scale is available. A missing time scale could be due to supertree methods, morphological data, or molecular data which violates the molecular clock. Our analytic approach is, in particular, useful for the model with extinction, since simulations of birth-death processes which are conditioned on obtaining n extant species today are quite delicate. Further, simulations are very time consuming for big n under both models.

SPECIATION OF ORGANICS IN WATER WITH RAMAN SPECTROSCOPY: UTILITY OF IONIC STRENGTH VARIATION

EPA Science Inventory

We have developed and are applying an experimental and mathematical method for describing the micro-speciation of complex organic contaminants in aqueous media. For our case, micro-speciation can be defined as qualitative and quantitative identification of all discrete forms of ...

CRYOGENIC TRAPPING OF OXIDIZED MERCURY SPECIES FROM COMBUSTION FLUE GAS. (R827649)

EPA Science Inventory

To further understand the speciation and partitioning of mercury species in combustion systems, it is necessary to be able to identify and quantitate the various forms of oxidized mercury. Currently accepted methods for speciating mercury (Ontario Hydro Method, EPA Method 29, ...

Comparative tests of the role of dewlap size in Anolis lizard speciation

PubMed Central

Harrison, Alexis; Mahler, D. Luke; Castañeda, María del Rosario; Glor, Richard E.; Herrel, Anthony; Stuart, Yoel E.; Losos, Jonathan B.

2016-01-01

Phenotypic traits may be linked to speciation in two distinct ways: character values may influence the rate of speciation or diversification in the trait may be associated with speciation events. Traits involved in signal transmission, such as the dewlap of Anolis lizards, are often involved in the speciation process. The dewlap is an important visual signal with roles in species recognition and sexual selection, and dewlaps vary among species in relative size as well as colour and pattern. We compile a dataset of relative dewlap size digitized from photographs of 184 anole species from across the genus' geographical range. We use phylogenetic comparative methods to test two hypotheses: that larger dewlaps are associated with higher speciation rates, and that relative dewlap area diversifies according to a speciational model of evolution. We find no evidence of trait-dependent speciation, indicating that larger signals do not enhance any role the dewlap has in promoting speciation. Instead, we find a signal of mixed speciational and gradual trait evolution, with a particularly strong signal of speciational change in the dewlaps of mainland lineages. This indicates that dewlap size diversifies in association with the speciation process, suggesting that divergent selection may play a role in the macroevolution of this signalling trait. PMID:28003450

Extensive range overlap between heliconiine sister species: evidence for sympatric speciation in butterflies?

PubMed

Rosser, Neil; Kozak, Krzysztof M; Phillimore, Albert B; Mallet, James

2015-06-30

Sympatric speciation is today generally viewed as plausible, and some well-supported examples exist, but its relative contribution to biodiversity remains to be established. We here quantify geographic overlap of sister species of heliconiine butterflies, and use age-range correlations and spatial simulations of the geography of speciation to infer the frequency of sympatric speciation. We also test whether shifts in mimetic wing colour pattern, host plant use and climate niche play a role in speciation, and whether such shifts are associated with sympatry. Approximately a third of all heliconiine sister species pairs exhibit near complete range overlap, and analyses of the observed patterns of range overlap suggest that sympatric speciation contributes 32%-95% of speciation events. Müllerian mimicry colour patterns and host plant choice are highly labile traits that seem to be associated with speciation, but we find no association between shifts in these traits and range overlap. In contrast, climatic niches of sister species are more conserved. Unlike birds and mammals, sister species of heliconiines are often sympatric and our inferences using the most recent comparative methods suggest that sympatric speciation is common. However, if sister species spread rapidly into sympatry (e.g. due to their similar climatic niches), then assumptions underlying our methods would be violated. Furthermore, although we find some evidence for the role of ecology in speciation, ecological shifts did not show the associations with range overlap expected under sympatric speciation. We delimit species of heliconiines in three different ways, based on "strict and " "relaxed" biological species concepts (BSC), as well as on a surrogate for the widely-used "diagnostic" version of the phylogenetic species concept (PSC). We show that one reason why more sympatric speciation is inferred in heliconiines than in birds may be due to a different culture of species delimitation in the two groups. To establish whether heliconiines are exceptional will require biogeographic comparative studies for a wider range of animal taxa including many more invertebrates.

Coupling pervaporation to AAS for inorganic and organic mercury determination. A new approach to speciation of Hg in environmental samples.

PubMed

Fernandez-Rivas, C; Muñoz-Olivas, R; Camara, C

2001-12-01

The design and development of a new approach for Hg speciation in environmental samples is described in detail. This method, consisting of the coupling of pervaporation and atomic absorption spectrometry, is based on a membrane phenomenon that combines the evaporation of volatile analytes and their diffusion through a polymeric membrane. It is proposed here as an alternative to gas chromatography for speciation of inorganic and organic Hg compounds, as the latter compounds are volatile and can be separated by applying the principles mentioned above. The interest of this method lies in its easy handling, low cost, and rapidity for the analysis of liquid and solid samples. This method has been applied to Hg speciation in a compost sample provided by a waste water treatment plant.

Detection of multiple Mycoplasma species in bulk tank milk samples using real-time PCR and conventional culture and comparison of test sensitivities.

PubMed

Justice-Allen, A; Trujillo, J; Goodell, G; Wilson, D

2011-07-01

The objective of this study was to further validate a SYBR PCR protocol for Mycoplasma spp. by comparing it with standard microbial culture in the detection of Mycoplasma spp. in bulk tank milk samples. Additionally, we identified Mycoplasma spp. present by analysis of PCR-generated amplicons [dissociation (melt) temperature (T(m)), length, and DNA sequence]. The research presented herein tests the hypothesis that the SYBR PCR protocol is as sensitive as conventional culture for the detection of Mycoplasma spp. in bulk tank milk samples. Mycoplasmas cause several important disease syndromes in cattle, including mastitis in dairy cows. The standard diagnostic method at the herd level has been microbial isolation of mycoplasmas on 1 of several specialized media and speciation through biochemical or immunological techniques; repeated sampling schemes are recommended. The development of a real-time SYBR PCR protocol offers advantages in decrease of time to detection, cost, and complexity. The T(m) of the double-stranded DNA generated from the PCR reaction was used to detect the presence of and tentatively identify the species of mycoplasmas other than Mycoplasma bovis. In the SYBR PCR protocol, the presence of multiple species of mycoplasmas is indicated by an atypical dissociation curve. Gel electrophoresis and sequencing of the amplicons was used to confirm the mycoplasma species present when a non-M. bovis organism was detected (T(m) not equal to M. bovis) and used to identify all the mycoplasma species present for the samples with atypical dissociation curves. Mycoplasma bovis was identified in 83% of SYBR PCR mycoplasma-positive bulk tank samples. Another mycoplasma was identified either alone or in addition to M. bovis in 25% of SYBR PCR mycoplasma-positive bulk tank milk samples. Four species of mycoplasma other than M. bovis (Mycoplasma alkalescens, Mycoplasma arginini, Mycoplasma bovigenitalium, and Mycoplasma gateae) were identified in bulk tank milk samples tested with this method. Five farms had 2 mycoplasma species occurring at different times in their bulk tanks. Two mycoplasma species were identified in the same bulk tank sample in 7 instances on 2 farms. The finding of multiple Mycoplasma spp. coexisting on a farm and even in the same bulk tank milk sample indicates that the clinical significance of multiple mycoplasma species in the pathology of intramammary infections should be investigated further. In comparison with conventional culture, the SYBR PCR protocol was slightly (but not statistically significantly) more sensitive in the detection of mycoplasmas in bulk tank milk. Copyright © 2011 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Does Diffusion Sequester Heavy Metals in Old Contamination Soils?

NASA Astrophysics Data System (ADS)

Ma, J.; Jennings, A. A.

2002-12-01

Old soil contamination refers to soil contamination that has aged over a long period of time. For example, at some brownfields, the soil heavy metal contamination can be one hundred or more years old. When contamination is young, the heavy metals are bound relatively weakly to the soil. However, the speciation and/or mechanisms of association evolve with aging into much more stable forms. It also appears that the metals migrate deeper into the bulk soil matrix where they are less available to participate in surface-related phenomena. Previous research showed elevated heavy metal extraction result after the soil was pulverized, with all other experiment conditions remaining unchanged. This indicates the presence of sequestered heavy metal contamination within the large soil particles (aggregate). The mechanisms of sequestering are uncertain, but diffusion appears to be a major factor. There are two possible pathways of diffusion that can account for heavy metal sequestering: solid-state diffusion through the bulk aggregate or liquid-phase diffusion through micro-pores within the aggregate structure. The second diffusion mechanism can be coupled with sorption (or other surface-related phenomena) on the pore walls. The remediation of sequestered heavy metals is also impacted by diffusion. Grinding a soil significantly reduces its average particle size. This exposes more of its internal bulk volume to extraction and results in much shorter diffusion pathway for the sequestered heavy metals to be released. Evidence has illustrated that this both improves remediation efficiency and provides a method by which the degree of sequestering can be quantified. This paper will present the results of ongoing research that is developing methods to identify the mechanisms of, quantify the magnitude of and determine the relative importance of (i.e. risk analysis) heavy metals sequestered in old contamination soils.

Speciation of PM10 sources of airborne nonferrous metals within the 3-km zone of lead/zinc smelters.

PubMed

Batonneau, Yann; Bremard, Claude; Gengembre, Leon; Laureyns, Jacky; Le Maguer, Agnes; Le Maguer, Didier; Perdrix, Esperanza; Sobanska, Sophie

2004-10-15

The purpose of this study was to estimate the speciation of PM10 sources of airborne Pb, Zn, and Cd metals (PM10 is an aerosol standard of aerodynamic diameter less than 10 microm.) in the atmosphere of a 3 km zone surrounding lead/zinc facilities in operation for a century. Many powdered samples were collected in stacks of working units (grilling, furnace, and refinery), outdoor storages (ores, recycled materials), surrounding waste slag (4 Mt), and polluted topsoils (3 km). PM10 samples were generated from the raw powders by using artificial resuspension and collection devices. The bulk PM10 multielemental analyses were determined by inductively coupled plasma-atomic emission spectrometry (ICP-AES). The proportions in mass of Pb (50%), Zn (40%), and Cd (1%) contents and associated metals (traces) reach the proportions of corresponding raw powdered samples of ores, recycled materials, and fumesize emissions of plants without specific enrichment. In contrast, Pb (8%) and Zn (15%) contents of PM10 of slag deposit were found to be markedly higher than those of raw dust, Pb (4%), and Zn (9%), respectively. In the same way, Pb (0.18%), Zn (0.20%), and Cd (0.004%) were enriched by 1.7, 2.1, and 2.3 times, respectively, in PM10 as compared with raw top-soil corresponding values. X-ray wavelength dispersive electron-microprobe (EM-WDS) microanalysis did not indicate well-defined phases or simple stoichiometries of all the PM10 samples atthe level of the spatial resolution (1 microm3). X-ray photoelectron spectroscopy (XPS) indicated that minor elements such as Cd, Hg, and C are more concentrated on the particle surface than in the bulk of PM10 generated by the smelting processes. (XPS) provided also the average speciation of the surface of PM10; Pb is mainly represented as PbSO4, Zn as ZnS, and Cd as CdS or CdSO4, and small amounts of coke were also detected. The speciation of bulk PM10 crystallized compounds was deduced from XRD diffractograms with a raw estimation of the relative quantities. PbS and ZnS were found to be the major phases in PM10 generated by the smelting facilities with PbSO4, PbSO4 x PbO, PbSO4 x 4PbO, Pb metal, and ZnO as minor phases. The slag waste PM10 was found to contain some amounts of PbCO3, PbSO4 x PbO, and ZnFe2O4 phases. The large heterogeneity at the level of the individual particle generates severe overlap of chemical information even at the microm scale using electron microprobe (WDS) and Raman microprobe techniques. Fortunately, scanning Raman microspectrometry combined with SIMPle-to-use Interactive Self-modeling Mixture Analysis (SIMPLISMA) performed the PM10 speciation at the level of individual particles. The speciation of major Pb, Zn, and Cd compounds of PM10 stack emissions and wind blown dust of ores and recycled materials were found to be PbSO4, PbSO4 x PbO, PbSO4 x 4PbO, PbO, metallic Pb, ZnS, ZnO, and CdS. The PM10 dust of slag waste was found to contain PbCO3, Pb(OH)2 x 2PbCO3, PbSO4 x PbO, and ZnS, while PM10-bound Pb, Zn of the top-soils contain Pb5(PO4)3Cl, ZnFe2O4 as well as Pb(II) and Zn(II) compounds adsorbed on Fe(III) oxides and in association with clays.

Living organisms as an alternative to hyphenated techniques for metal speciation. Evaluation of baker's yeast immobilized on silica gel for Hg speciation*1

NASA Astrophysics Data System (ADS)

Pérez-Corona, Teresa; Madrid-Albarrán, Yolanda; Cámara, Carmen; Beceiro, Elisa

1998-02-01

The use of living organisms for metal preconcentration and speciation is discussed. Among substrates, Saccharomyces cerevisiae baker's yeast has been successfully used for the speciation of mercury [Hg(II) and CH 3Hg +], selenium [Se(IV) and Se(VI)] and antimony [Sb(III) and Sb(V)]. To illustrate the capabilities of these organisms, the analytical performance of baker's yeast immobilized on silica gel for on-line preconcentration and speciation of Hg(II) and methylmercury is reported. The immobilized cells were packed in a PTFE microcolumn, through which mixtures of organic and inorganic mercury solutions were passed. Retention of inorganic and organic mercury solutions took place simultaneously, with the former retained in the silica and the latter on the yeast. The efficiency uptake for both species was higher than 95% over a wide pH range. The speciation was carried out by selective and sequential elution with 0.02 mol L -1 HCl for methylmercury and 0.8 mol L -1 CN - for Hg(II). This method allows both preconcentration and speciation of mercury. The preconcentration factors were around 15 and 100 for methylmercury and mercury(II), respectively. The method has been successfully applied to spiked sea water samples.

Considerations in As analysis and speciation

USGS Publications Warehouse

Edwards, M.; Patel, S.; McNeil, L.; Chen, H.W.; Frey, M.; Eaton, A.D.; Antweiler, Ronald C.; Taylor, Howard E.

1998-01-01

This article summarizes recent experiences in arsenic (As) quantification, preservation, and speciation developed during AWWA Research Foundation (AWWARF) and Water Industry Technical Action Fund (WITAF) projects. The goal of this article is to alert analysts and decision-makers to potential problems in As analysis and speciation, because there appear to be several unresolved problems with routine analytical approaches. In true split drinking water samples As was quantified by three accepted analytical methods in three laboratories. The techniques used were graphite furnace atomic absorption spectrometry (GFAAS), inductively coupled plasma mass spectrometry (ICP-MS), and hydride generation inductively coupled plasma-emission spectrometry (HG-ICP-AES). Experimental findings are organized into sections on As analysis, particulate As in water supplies, and examination of As speciation methods.

Speciation and amphotericin B sensitivity studies on blood isolates of Candida from burned patients

PubMed Central

Stieritz, Donald D.; Law, Edward J.; Holder, Ian Alan

1973-01-01

Methods of speciating Candida isolates from clinical specimens are described and the necessity of speciation is emphasized. Differences in susceptibility of C. albicans and C. tropicalis to amphotericin B were observed and the implications of this in relation to treatment with amphotericin B and the development of resistance are discussed. PMID:4578160

Use of X-Ray Absorption Spectroscopy (XAS) to Speciate Manganese in Airborne Particulate Matter from 5 Counties Across the US

PubMed Central

Datta, Saugata; Rule, Ana M; Mihalic, Jana N; Chillrud, Steve N; Bostick, Benjamin C.; Ramos-Bonilla, Juan P; Han, Inkyu; Polyak, Lisa M; Geyh, Alison S; Breysse, Patrick N

2012-01-01

The purpose of this study is to characterize manganese oxidation states and speciation in airborne particulate matter (PM), and describe how these potentially important determinants of PM toxicity vary by location. Ambient PM samples were collected from five counties across the US using a high volume sequential cyclone system that collects PM in dry bulk form segregated into “coarse” and “fine” size fractions. The fine fraction was analyzed for this study. Analyses included total Mn using ICP-MS, and characterization of oxidation states and speciation using X-ray Absorption Spectroscopy (XAS). XAS spectra of all samples and ten standard compounds of Mn were obtained at the National Synchrotron Light Source. XAS data was analyzed using Linear Combination Fitting (LCF). Results of the LCF analysis describe differences in composition between samples. Mn(II) acetate and Mn(II) oxide are present in all samples, while Mn(II) carbonate and Mn(IV) oxide are absent. To the best of our knowledge, this is the first paper to characterize Mn composition of ambient PM and examine differences between urban sites in the US. Differences in oxidation state and composition indicate regional variations in sources and atmospheric chemistry that may help explain differences in health effects identified in epidemiological studies. PMID:22309075

Selenium Speciation and Management in Wet FGD Systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Searcy, K; Richardson, M; Blythe, G

2012-02-29

This report discusses results from bench- and pilot-scale simulation tests conducted to determine the factors that impact selenium speciation and phase partitioning in wet FGD systems. The selenium chemistry in wet FGD systems is highly complex and not completely understood, thus extrapolation and scale-up of these results may be uncertain. Control of operating parameters and application of scrubber additives have successfully demonstrated the avoidance or decrease of selenite oxidation at the bench and pilot scale. Ongoing efforts to improve sample handling methods for selenium speciation measurements are also discussed. Bench-scale scrubber tests explored the impacts of oxidation air rate, tracemore » metals, scrubber additives, and natural limestone on selenium speciation in synthetic and field-generated full-scale FGD liquors. The presence and concentration of redox-active chemical species as well as the oxidation air rate contribute to the oxidation-reduction potential (ORP) conditions in FGD scrubbers. Selenite oxidation to the undesirable selenate form increases with increasing ORP conditions, and decreases with decreasing ORP conditions. Solid-phase manganese [Mn(IV)] appeared to be the significant metal impacting the oxidation of selenite to selenate. Scrubber additives were tested for their ability to inhibit selenite oxidation. Although dibasic acid and other scrubber additives showed promise in early clear liquor (sodium based and without calcium solids) bench-scale tests, these additives did not show strong inhibition of selenite oxidation in tests with higher manganese concentrations and with slurries from full-scale wet FGD systems. In bench-tests with field liquors, addition of ferric chloride at a 250:1 iron-to-selenium mass ratio sorbed all incoming selenite to the solid phase, although addition of ferric salts had no impact on native selenate that already existed in the field slurry liquor sample. As ORP increases, selenite may oxidize to selenate more rapidly than it sorbs to ferric solids. Though it was not possible to demonstrate a decrease in selenium concentrations to levels below the project'ale testing were evident at the pilot scale. Specifically, reducing oxidation air rate and ORP tends to either retain selenium as selenite in the liquor or shift selenium phase partitioning to the solid phase. Oxidation air flow rate control may be one option for managing selenium behavior in FGD scrubbers. Units that cycle load widely may find it more difficult to impact ORP conditions with oxidation air flow rate control alone. Because decreasing oxidation air rates to the reaction tank showed that all new selenium reported to the solids, the addition of ferric chloride to the pilot scrubber could not show further improvements in selenium behavior. Ferric chloride addition did shift mercury to the slurry solids, specifically to the fine particles. Several competing pathways may govern the reporting of selenium to the slurry solids: co-precipitation with gypsum into the bulk solids and sorption or co-precipitation with iron into the fine particles. Simultaneous measurement of selenium and mercury behavior suggests a holistic management strategy is best to optimize the fate of both of these elements in FGD waters. Work conducted under this project evaluated sample handling and analytical methods for selenium speciation in FGD waters. Three analytical techniques and several preservation methods were employed. Measurements of selenium speciation over time indicated that for accurate selenium speciation, it is best to conduct measurements on unpreserved, filtered samples as soon after sampling as possible. The capital and operating costs for two selenium management strategies were considered: ferric chloride addition and oxidation air flow rate control. For ferric chloride addition, as might be expected the reagent makeup costs dominate the overall costs, and range from 0.22 to 0.29 mills/kWh. For oxidation air flow rate control, a cursory comparison of capital costs and turndown capabilities for multi-stage and single-stage centrifugal blowers and several flow control methods was completed. For greenfield systems, changing the selection of blower type and flow control method may have payback periods of 4 to 5 years or more if based on energy savings alone. However, the benefits to managing redox chemistry in the scrubber could far outweigh the savings in electricity costs under some circumstances.« less

A study of method robustness for arsenic speciation in drinking water samples by anion exchange HPLC-ICP-MS.

PubMed

Day, Jason A; Montes-Bayón, María; Vonderheide, Anne P; Caruso, Joseph A

2002-08-01

Regulating arsenic species in drinking waters is a reasonable objective, since the various species have different toxicological impacts. However, developing robust and sensitive speciation methods is mandatory prior to any such regulations. Numerous arsenic speciation publications exist, but the question of robustness or ruggedness for a regulatory method has not been fully explored. The present work illustrates the use of anion exchange chromatography coupled to ICP-MS with a commercially available "speciation kit" option. The mobile phase containing 2 mM NaH(2)PO(4) and 0.2 mM EDTA at pH 6 allowed adequate separation of four As species (As(III), As(V), MMAA, DMAA) in less than 10 min. The analytical performance characteristics studied, including method detection limits (lower than 100 ng L(-1) for all the species evaluated), proved the suitability of the method to fulfill the current regulation. Other parameters evaluated such as laboratory fortified blanks, spiked recoveries, and reproducibility over a certain period of time produced adequate results. The samples analyzed were taken from water utilities in different areas of the United States and were provided by the U.S. EPA. The data suggests the speciation setup performs to U.S. EPA specifications but sample treatment and chemistry are also important factors for achieving good recoveries for samples spiked with As(III) as arsenite and As(V) as arsenate.

Martian regolith in Elephant Moraine 79001 shock melts? Evidence from major element composition and sulfur speciation

NASA Astrophysics Data System (ADS)

Walton, E. L.; Jugo, P. J.; Herd, C. D. K.; Wilke, M.

2010-08-01

Shock veins and melt pockets in Lithology A of Martian meteorite Elephant Moraine (EETA) 79001 have been investigated using electron microprobe (EM) analysis, petrography and X-ray Absorption Near Edge Structure (XANES) spectroscopy to determine elemental abundances and sulfur speciation (S 2- versus S 6+). The results constrain the materials that melted to form the shock glasses and identify the source of their high sulfur abundances. The XANES spectra for EETA79001 glasses show a sharp peak at 2.471 keV characteristic of crystalline sulfides and a broad peak centered at 2.477 keV similar to that obtained for sulfide-saturated glass standards analyzed in this study. Sulfate peaks at 2.482 keV were not observed. Bulk compositions of EETA79001 shock melts were estimated by averaging defocused EM analyses. Vein and melt pocket glasses are enriched in Al, Ca, Na and S, and depleted in Fe, Mg and Cr compared to the whole rock. Petrographic observations show preferential melting and mobilization of plagioclase and pyrrhotite associated with melt pocket and vein margins, contributing to the enrichments. Estimates of shock melt bulk compositions obtained from glass analyses are biased towards Fe- and Mg- depletions because, in general, basaltic melts produced from groundmass minerals (plagioclase and clinopyroxene) will quench to a glass, whereas ultramafic melts produced from olivine and low-Ca pyroxene megacrysts crystallize during the quench. We also note that the bulk composition of the shock melt pocket cannot be determined from the average composition of the glass but must also include the crystals that grew from the melt - pyroxene (En 72-75Fs 20-21Wo 5-7) and olivine (Fo 75-80). Reconstruction of glass + crystal analyses gives a bulk composition for the melt pocket that approaches that of lithology A of the meteorite, reflecting bulk melting of everything except xenolith chromite. Our results show that EETA79001 shock veins and melt pockets represent local mineral melts formed by shock impedance contrasts, which can account for the observed compositional anomalies compared to the whole rock sample. The observation that melts produced during shock commonly deviate from the bulk composition of the host rock has been well documented from chondrites, rocks from terrestrial impact structures and other Martian meteorites. The bulk composition of shock melts reflects the proportions of minerals melted; large melt pockets encompass more minerals and approach the whole rock whereas small melt pockets and thin veins reflect local mineralogy. In the latter, the modal abundance of sulfide globules may reach up to 15 vol%. We conclude the shock melt pockets in EETA79001 lithology A contain no significant proportion of Martian regolith.

Foliar or root exposures to smelter particles: consequences for lead compartmentalization and speciation in plant leaves.

PubMed

Schreck, Eva; Dappe, Vincent; Sarret, Géraldine; Sobanska, Sophie; Nowak, Dorota; Nowak, Jakub; Stefaniak, Elżbieta Anna; Magnin, Valérie; Ranieri, Vincent; Dumat, Camille

2014-04-01

In urban areas with high fallout of airborne particles, metal uptake by plants mainly occurs by foliar pathways and can strongly impact crop quality. However, there is a lack of knowledge on metal localization and speciation in plants after pollution exposure, especially in the case of foliar uptake. In this study, two contrasting crops, lettuce (Lactuca sativa L.) and rye-grass (Lolium perenne L.), were exposed to Pb-rich particles emitted by a Pb-recycling factory via either atmospheric or soil application. Pb accumulation in plant leaves was observed for both ways of exposure. The mechanisms involved in Pb uptake were investigated using a combination of microscopic and spectroscopic techniques (electron microscopy, laser ablation, Raman microspectroscopy, and X-ray absorption spectroscopy). The results show that Pb localization and speciation are strongly influenced by the type of exposure (root or shoot pathway) and the plant species. Foliar exposure is the main pathway of uptake, involving the highest concentrations in plant tissues. Under atmospheric fallouts, Pb-rich particles were strongly adsorbed on the leaf surface of both plant species. In lettuce, stomata contained Pb-rich particles in their apertures, with some deformations of guard cells. In addition to PbO and PbSO4, chemical forms that were also observed in pristine particles, new species were identified: organic compounds (minimum 20%) and hexagonal platy crystals of PbCO3. In rye-grass, the changes in Pb speciation were even more egregious: Pb-cell wall and Pb-organic acid complexes were the major species observed. For root exposure, identified here as a minor pathway of Pb transfer compared to foliar uptake, another secondary species, pyromorphite, was identified in rye-grass leaves. Finally, combining bulk and spatially resolved spectroscopic techniques permitted both the overall speciation and the minor but possibly highly reactive lead species to be determined in order to better assess the health risks involved. Copyright © 2013 Elsevier B.V. All rights reserved.

Including the spatial variability of metal speciation in the effect factor in life cycle impact assessment: Limits of the equilibrium partitioning method.

PubMed

Tromson, Clara; Bulle, Cécile; Deschênes, Louise

2017-03-01

In life cycle assessment (LCA), the potential terrestrial ecotoxicity effect of metals, calculated as the effect factor (EF), is usually extrapolated from aquatic ecotoxicological data using the equilibrium partitioning method (EqP) as it is more readily available than terrestrial data. However, when following the AMI recommendations (i.e. with at least enough species that represents three different phyla), there are not enough terrestrial data for which soil properties or metal speciation during ecotoxicological testing are specified to account for the influence of soil property variations on metal speciation when using this approach. Alternatively, the TBLM (Terrestrial Biotic Ligand Model) has been used to determine an EF that accounts for speciation, but is not available for metals; hence it cannot be consistently applied to metals in an LCA context. This paper proposes an approach to include metal speciation by regionalizing the EqP method for Cu, Ni and Zn with a geochemical speciation model (the Windermere Humic Aqueous Model 7.0), for 5213 soils selected from the Harmonized World Soil Database. Results obtained by this approach (EF EqP regionalized ) are compared to the EFs calculated with the conventional EqP method, to the EFs based on available terrestrial data and to the EFs calculated with the TBLM (EF TBLM regionalized ) when available. The spatial variability contribution of the EF to the overall spatial variability of the characterization factor (CF) has been analyzed. It was found that the EFs EqP regionalized show a significant spatial variability. The EFs calculated with the two non-regionalized methods (EqP and terrestrial data) fall within the range of the EFs EqP regionalized . The EFs TBLM regionalized cover a larger range of values than the EFs EqP regionalized but the two methods are not correlated. This paper highlights the importance of including speciation into the terrestrial EF and shows that using the regionalized EqP approach is not an acceptable proxy for terrestrial ecotoxicological data even if it can be applied to all metals. Copyright © 2016. Published by Elsevier B.V.

Rapid radiation in spiny lobsters (Palinurus spp) as revealed by classic and ABC methods using mtDNA and microsatellite data.

PubMed

Palero, Ferran; Lopes, Joao; Abelló, Pere; Macpherson, Enrique; Pascual, Marta; Beaumont, Mark A

2009-11-09

Molecular tools may help to uncover closely related and still diverging species from a wide variety of taxa and provide insight into the mechanisms, pace and geography of marine speciation. There is a certain controversy on the phylogeography and speciation modes of species-groups with an Eastern Atlantic-Western Indian Ocean distribution, with previous studies suggesting that older events (Miocene) and/or more recent (Pleistocene) oceanographic processes could have influenced the phylogeny of marine taxa. The spiny lobster genus Palinurus allows for testing among speciation hypotheses, since it has a particular distribution with two groups of three species each in the Northeastern Atlantic (P. elephas, P. mauritanicus and P. charlestoni) and Southeastern Atlantic and Southwestern Indian Oceans (P. gilchristi, P. delagoae and P. barbarae). In the present study, we obtain a more complete understanding of the phylogenetic relationships among these species through a combined dataset with both nuclear and mitochondrial markers, by testing alternative hypotheses on both the mutation rate and tree topology under the recently developed approximate Bayesian computation (ABC) methods. Our analyses support a North-to-South speciation pattern in Palinurus with all the South-African species forming a monophyletic clade nested within the Northern Hemisphere species. Coalescent-based ABC methods allowed us to reject the previously proposed hypothesis of a Middle Miocene speciation event related with the closure of the Tethyan Seaway. Instead, divergence times obtained for Palinurus species using the combined mtDNA-microsatellite dataset and standard mutation rates for mtDNA agree with known glaciation-related processes occurring during the last 2 my. The Palinurus speciation pattern is a typical example of a series of rapid speciation events occurring within a group, with very short branches separating different species. Our results support the hypothesis that recent climate change-related oceanographic processes have influenced the phylogeny of marine taxa, with most Palinurus species originating during the last two million years. The present study highlights the value of new coalescent-based statistical methods such as ABC for testing different speciation hypotheses using molecular data.

Dissolved and labile concentrations of Cd, Cu, Pb, and Zn in the South Fork Coeur d'Alene River, Idaho: Comparisons among chemical equilibrium models and implications for biotic ligand models

USGS Publications Warehouse

Balistrieri, L.S.; Blank, R.G.

2008-01-01

In order to evaluate thermodynamic speciation calculations inherent in biotic ligand models, the speciation of dissolved Cd, Cu, Pb, and Zn in aquatic systems influenced by historical mining activities is examined using equilibrium computer models and the diffusive gradients in thin films (DGT) technique. Several metal/organic-matter complexation models, including WHAM VI, NICA-Donnan, and Stockholm Humic model (SHM), are used in combination with inorganic speciation models to calculate the thermodynamic speciation of dissolved metals and concentrations of metal associated with biotic ligands (e.g., fish gills). Maximum dynamic metal concentrations, determined from total dissolved metal concentrations and thermodynamic speciation calculations, are compared with labile metal concentrations measured by DGT to assess which metal/organic-matter complexation model best describes metal speciation and, thereby, biotic ligand speciation, in the studied systems. Results indicate that the choice of model that defines metal/organic-matter interactions does not affect calculated concentrations of Cd and Zn associated with biotic ligands for geochemical conditions in the study area, whereas concentrations of Cu and Pb associated with biotic ligands depend on whether the speciation calculations use WHAM VI, NICA-Donnan, or SHM. Agreement between labile metal concentrations and dynamic metal concentrations occurs when WHAM VI is used to calculate Cu speciation and SHM is used to calculate Pb speciation. Additional work in systems that contain wide ranges in concentrations of multiple metals should incorporate analytical speciation methods, such as DGT, to constrain the speciation component of biotic ligand models. ?? 2008 Elsevier Ltd.

Impact of intracellular metallothionein on metal biouptake and partitioning dynamics at bacterial interfaces.

PubMed

Présent, Romain M; Rotureau, Elise; Billard, Patrick; Pagnout, Christophe; Sohm, Bénédicte; Flayac, Justine; Gley, Renaud; Pinheiro, José P; Duval, Jérôme F L

2017-11-08

Genetically engineered microorganisms are alternatives to physicochemical methods for remediation of metal-contaminated aquifers due to their remarkable bioaccumulation capacities. The design of such biosystems would benefit from the elaboration of a sound quantitative connection between performance in terms of metal removal from aqueous solution and dynamics of the multiscale processes leading to metal biouptake. In this work, this elaboration is reported for Escherichia coli cells modified to overexpress intracellular metallothionein (MTc), a strong proteinaceous metal chelator. Depletion kinetics of Cd(ii) from bulk solution following biouptake and intracellular accumulation is addressed as a function of cell volume fraction using electroanalytical probes and ligand exchange-based analyses. It is shown that metal biouptake in the absence and presence of MTc is successfully interpreted on the basis of a formalism recently developed for metal partitioning dynamics at biointerfaces with integration of intracellular metal speciation. The analysis demonstrates how fast sequestration of metals by intracellular MTc bypasses metal excretion (efflux) and enhances the rate of metal depletion to an extent such that complete removal is achieved at sufficiently large cell volume fractions. The magnitude of the stability constant of nanoparticulate metal-MTc complexes, as derived from refined analysis of macroscopic bulk metal depletion data, is further confirmed by independent electrochemical measurement of metal binding by purified MTc extracts.

Vertical changes of the Co and Mn speciation along a lateritic regolith developed on peridotites (New Caledonia)

DOE PAGES

Dublet, Gabrielle; Juillot, Farid; Brest, Jessica; ...

2017-07-21

Because they can host significant amounts of Co, the Mn-oxides are commonly considered as the major Co-bearing mineral species in lateritic environments. However, little is known about the process leading to the formation and/or the weathering of these Co-rich Mn-oxides. This lack of knowledge is mainly due to the fact that Co concentrations are too low in primary silicates for classical speciation analysis. In this study, we investigated both Co and Mn speciation in a 64 m thick lateritic regolith developed upon peridotites in New Caledonia, by combining High Energy Resolution Fluorescence Detection X-ray absorption Near Edge Structure (HERFD-XANES) spectroscopymore » at the Co K-edge with classical XANES spectroscopy at the Mn K-edge, bulk chemistry (ICP) and mineralogy (XRD). The results obtained provide new insights into the evolution of Co and Mn speciation as a function of the weathering stages. Co and Mn primarily occur as Co(II) and Mn(II,III) in olivine and serpentine in the bedrock. During the first weathering stage, these forms of Co and Mn are progressively oxidized toward Co(III) and Mn(III,IV), which occur mainly as Co(III)-bearing Mn(III/IV)-oxides in the transition between the saprolite and the laterite. In the uppermost lateritic horizons, long-time weathering resulted in a strong leaching of Co and Mn, and the remaining of these elements occurs as Co(II) and Mn(III) substituting for Fe(III) in goethite. Finally, this latter scavenging process emphasizes the importance of Fe-oxides for the long-term stabilization of Co and Mn in such deeply weathered laterites.« less

Vertical changes of the Co and Mn speciation along a lateritic regolith developed on peridotites (New Caledonia)

NASA Astrophysics Data System (ADS)

Dublet, Gabrielle; Juillot, Farid; Brest, Jessica; Noël, Vincent; Fritsch, Emmanuel; Proux, Olivier; Olivi, Luca; Ploquin, Florian; Morin, Guillaume

2017-11-01

Because they can host significant amounts of Co, the Mn-oxides are commonly considered as the major Co-bearing mineral species in lateritic environments. However, little is known about the process leading to the formation and/or the weathering of these Co-rich Mn-oxides. This lack of knowledge is mainly due to the fact that Co concentrations are too low in primary silicates for classical speciation analysis. In this study, we investigated both Co and Mn speciation in a 64 m thick lateritic regolith developed upon peridotites in New Caledonia, by combining High Energy Resolution Fluorescence Detection X-ray absorption Near Edge Structure (HERFD-XANES) spectroscopy at the Co K-edge with classical XANES spectroscopy at the Mn K-edge, bulk chemistry (ICP) and mineralogy (XRD). The results obtained provide new insights into the evolution of Co and Mn speciation as a function of the weathering stages. Co and Mn primarily occur as Co(II) and Mn(II,III) in olivine and serpentine in the bedrock. During the first weathering stage, these forms of Co and Mn are progressively oxidized toward Co(III) and Mn(III,IV), which occur mainly as Co(III)-bearing Mn(III/IV)-oxides in the transition between the saprolite and the laterite. In the uppermost lateritic horizons, long-time weathering resulted in a strong leaching of Co and Mn, and the remaining of these elements occurs as Co(II) and Mn(III) substituting for Fe(III) in goethite. This latter scavenging process emphasizes the importance of Fe-oxides for the long-term stabilization of Co and Mn in such deeply weathered laterites.

A speciation solver for cement paste modeling and the semismooth Newton method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Georget, Fabien, E-mail: fabieng@princeton.edu; Prévost, Jean H., E-mail: prevost@princeton.edu; Vanderbei, Robert J., E-mail: rvdb@princeton.edu

2015-02-15

The mineral assemblage of a cement paste may vary considerably with its environment. In addition, the water content of a cement paste is relatively low and the ionic strength of the interstitial solution is often high. These conditions are extreme conditions with respect to the common assumptions made in speciation problem. Furthermore the common trial and error algorithm to find the phase assemblage does not provide any guarantee of convergence. We propose a speciation solver based on a semismooth Newton method adapted to the thermodynamic modeling of cement paste. The strong theoretical properties associated with these methods offer practical advantages.more » Results of numerical experiments indicate that the algorithm is reliable, robust, and efficient.« less

Selenium Metabolism in Cancer Cells: The Combined Application of XAS and XFM Techniques to the Problem of Selenium Speciation in Biological Systems

PubMed Central

Weekley, Claire M.; Aitken, Jade B.; Finney, Lydia; Vogt, Stefan; Witting, Paul K.; Harris, Hugh H.

2013-01-01

Determining the speciation of selenium in vivo is crucial to understanding the biological activity of this essential element, which is a popular dietary supplement due to its anti-cancer properties. Hyphenated techniques that combine separation and detection methods are traditionally and effectively used in selenium speciation analysis, but require extensive sample preparation that may affect speciation. Synchrotron-based X-ray absorption and fluorescence techniques offer an alternative approach to selenium speciation analysis that requires minimal sample preparation. We present a brief summary of some key HPLC-ICP-MS and ESI-MS/MS studies of the speciation of selenium in cells and rat tissues. We review the results of a top-down approach to selenium speciation in human lung cancer cells that aims to link the speciation and distribution of selenium to its biological activity using a combination of X-ray absorption spectroscopy (XAS) and X-ray fluorescence microscopy (XFM). The results of this approach highlight the distinct fates of selenomethionine, methylselenocysteine and selenite in terms of their speciation and distribution within cells: organic selenium metabolites were widely distributed throughout the cells, whereas inorganic selenium metabolites were compartmentalized and associated with copper. New data from the XFM mapping of electrophoretically-separated cell lysates show the distribution of selenium in the proteins of selenomethionine-treated cells. Future applications of this top-down approach are discussed. PMID:23698165

ARSENIC SPECIATION ANALYSIS IN HUMAN SALIVA

EPA Science Inventory

Background: Determination of arsenic species in human saliva is potentially useful for biomonitoring of human exposure to arsenic and for studying arsenic metabolism. However, there is no report on the speciation analysis of arsenic in saliva. Methods: Arsenic species in saliva ...

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory; arsenic speciation in natural-water samples using laboratory and field methods

USGS Publications Warehouse

Garbarino, John R.; Bednar, Anthony J.; Burkhardt, Mark R.

2002-01-01

Analytical methods for the determination of arsenite [As(III)], arsenate [As(V)], dimethylarsinate (DMA), monomethylarsonate (MMA), and roxarsone in filtered natural-water samples are described. Various analytical methods can be used for the determination, depending on the arsenic species being determined. Arsenic concentration is determined by using inductively coupled plasma-mass spectrometry (ICP-MS) as an arsenic-specific detector for all methods. Laboratory-speciation methods are described that use an ion chromatographic column to separate the arsenic species; the column length, column packing, and mobile phase are dependent on the species of interest. Regardless of the separation technique, the arsenic species are introduced into plasma by eithe rpneumatic nebulization or arsine generation. Analysis times range from 2 to 8 minutes and method detection limits range from 0.1 to 0.6 microgram-arsenic per liter (ug-As/L), 10 to 60 picograms absolute (for a 100-microliter injection), depending on the arsenic species determined and the analytical method used. A field-generation specciation method also is described that uses a strong anion exchange cartridge to separate As(III) from As(V) in the field. As(III) in the eluate and the As(V) in the cartridge extract are determined by direct nebulization ICP-MS. Methylated arsenic species that also are retained on the cartridge will positively bias As(V) results without further laboratory separations. The method detection limit for field speciation is 0.3 ug-As/L. The distribution of arsenic species must be preserved in the field to eliminate changes caused by photochemical oxidation or metal oxyhydroxide precipitation. Preservation techniques, such as refrigeration, the addition of acides, or the additoin of ethylene-diaminetetraacetic acid (EDTA) and the effects of ambient light were tested. Of the preservatives evaluated, EDTA was found to work best with the laboratory- and field-speciation methods for all sample matrices tested. Storing the samples in opaque polytethylene bottles eliminated the effects of photochemical oxidation. The percentage change in As(III):As(V) ratios for an EDTA-preserved acid mine drainage (AMD) sample and ground-water sample during a 3-month period was -5 percent and +3 percent, respectively. The bias and variability of the methods were evaluated by comparing results for total arsenic and As(III), As(V), DMA, and MMA concentrations in ground water, AMD, and surface water. Seventy-one ground-water, 10 AMD, and 24 surface-water samples were analyzed. Concentrations in ground-water samples reached 720 ug-As/L for As(III) and 1080 ug-As/L for As(V); AMD samples reached 12800 ug-As/L for As(III) and 7050 ug-As/L for As(V); and surface-water samples reached 5 ug-As/L for As(III) and As(V). Inorganic arsenic species distribution in the samples ranged from 0 to 90 percent As(III). DMA and MMA were present only in surface-water samples from agricultural areas where the herbicide monosodium methylarsonate was applied; concentrations never exceeded 6 ug-As/L. Statistical analyses indicated that the difference between As(III) and As(V) concentrations for samples preserved with EDTA in opaque bottles and field-speciation results were analytically insignificant at the 95-percent confidence interval. There was no significant difference among the methods tested for total arsenic concentration. Percentage recovery for field samples spiked at 50 ug-As/L and analyzed by the laboratory-speciation method (n=2) ranged from 82 to 100 percent for As(III), 97 to 102 percent for As(V), 90 to 104 percent for DMA, and 81 to 96 percent for MMA; recoveries for samples spiked at 100 ug-As/L and analyzed by the field-speciation method ranged from 102 to 107 percent for As(III) and 105 to 106 percent for As(V). Laboratory-speciation results for Environment Canada reference material SLRS-2 closely matched reported concentrations. Laboratory-speciation metho

In-situ identification of iron electrocoagulation speciation and application for natural organic matter (NOM) removal.

PubMed

Dubrawski, Kristian L; Mohseni, Madjid

2013-09-15

In this work, iron speciation in electrocoagulation (EC) was studied to determine the impact of operating parameters on natural organic matter (NOM) removal from natural water. Two electrochemical EC parameters, current density (i) and charge loading rate (CLR), were investigated. Variation of these parameters led to a near unity current efficiency (φ = 0.957 ± 0.03), at any combination of i in a range of 1-25 mA/cm(2) and CLR in a range of 12-300 C/L/min. Higher i and CLR led to a higher bulk pH and limited the amount of dissolved oxygen (DO) reduced at the cathode surface due to mass transfer limitations. A low i (1 mA/cm(2)) and intermediate CLR (60 C/L/min) resulted in low bulk DO (<2.5 mg/L), where green rust (GR) was identified by in-situ Raman spectroscopy as the primary crystalline electrochemical product. Longer electrolysis times at higher i led to magnetite (Fe3O4) formation. Both higher (300 C/L/min) and lower (12 C/L/min) CLR values led to increased DO and/or increased pH, with lepidocrocite (γ-FeOOH) as the only crystalline species observed. The NOM removal of the three identified species was compared, with conditions leading to GR formation showing the greatest dissolved organic carbon removal, and highest removal of the low apparent molecular weight (<550 Da) chromophoric NOM fraction, determined by high performance size exclusion chromatography. Copyright © 2013 Elsevier Ltd. All rights reserved.

Sulfur Speciation in Peat: a Time-zero Signature for the " Spruce and Peatland Responses Under Climate and Environmental Change" Experiment

NASA Astrophysics Data System (ADS)

Furman, O.; Toner, B. M.; Sebestyen, S. D.; Kolka, R. K.; Nater, E. A.

2014-12-01

As part of the "Spruce and Peatland Responses Under Climate and Environmental Change" (SPRUCE) experiment, we made initial measurements of sulfur speciation in peat. These observations represent a "time-zero" relative to the intended soil warming experiment which begins in 2015. Total sulfur and sulfur speciation were measured in peat cores (solid phase) from nine plots (hollows and hummocks) to a depth of 2 m. Peat samples were packed under nitrogen and frozen in the field immediately after collection. All subsequent sample storage, handling, and processing were conducted under inert gas. Sulfur speciation was measured using bulk sulfur 1s X-ray absorption near edge structure (XANES) spectroscopy at the SXRMB instrument at the Canadian Light Source, Saskatoon, SK, Canada and at the 9-BM instrument, Advanced Photon Source, Argonne National Laboratory, IL, USA. Total sulfur concentrations ranged from 968 to 4077 mg sulfur / kg dry peat. Sulfur content increased with depth from 2 g sulfur / m2 in the 0-10 cm increment to a maximum value of 38 g sulfur / m2 in the 50-60 cm increment. These sulfur loadings produced high quality XANES spectra. The nine cores exhibited reproducible trends with depth in both total sulfur and specific sulfur species; however, variability in sulfur speciation was greatest in the top 40 cm. All sulfur detected within the peat solids was in an organic form. The most abundant sulfur species group was composed of organic mono-sulfide and thiol forms, representing approximately half of the total sulfur at all depths. Sulfonate and ester-sulfate species were 10-15 mol% of sulfur and exhibited low variability with depth. A subsurface maximum in organic di-sulfide was observed in the 20-30 cm depth increment, which is the transition zone between transiently oxidized acrotelm and permanently saturated anaerobic catotelm. Quantification of major sulfur pools is important for the SPRUCE experiment as they are likely to be indicators of changes in the oxidation-reduction (redox) status, and mercury methylation potential, of the peat in response to warming and enhanced carbon dioxide.

[The progress in speciation analysis of trace elements by atomic spectrometry].

PubMed

Wang, Zeng-Huan; Wang, Xu-Nuo; Ke, Chang-Liang; Lin, Qin

2013-12-01

The main purpose of the present work is to review the different non-chromatographic methods for the speciation analysis of trace elements in geological, environmental, biological and medical areas. In this paper, the sample processing methods in speciation analysis were summarized, and the main strategies for non-chromatographic technique were evaluated. The basic principles of the liquid extractions proposed in the published literatures recently and their advantages and disadvantages were discussed, such as conventional solvent extraction, cloud point extraction, single droplet microextraction, and dispersive liquid-liquid microextraction. Solid phase extraction, as a non-chromatographic technique for speciation analysis, can be used in batch or in flow detection, and especially suitable for the online connection to atomic spectrometric detector. The developments and applications of sorbent materials filled in the columns of solid phase extraction were reviewed. The sorbents include chelating resins, nanometer materials, molecular and ion imprinted materials, and bio-sorbents. Other techniques, e. g. hydride generation technique and coprecipitation, were also reviewed together with their main applications.

Metals, Health and the Environment – Emergence of Correlations Between Speciation and Effects

PubMed Central

Williams, David R.

2004-01-01

Over the last half-century both the identification of the causes of diseases and the use of inorganic compounds to treat such conditions have been considerably enlightened through our emerging capabilities to identify the pivotal chemical species involved. The ‘duty of care’ placed upon scientists to protect the environment from manufactured chemicals and to limit their effects upon humans therefrom is best realised from a speciation knowledge database. This paper discusses categorising chemicals in terms of their persistence, bioaccumulation, and toxicities and uses speciation information to optimise desirable effects of chemicals in several applications such as the manufacture of pulp for paper and in the foliar nutrition of crops. Simultaneously, the chemical wasting side effects of industrial overdosing is easily avoided if speciation approaches are used. The move towards new environmentally friendly ligand agents is described and methods of finding substitute agents (often combinations of two or more chemicals) to replace nonbiodegradable EDTA. The geosphere migration of metals through the environment is discussed in terms of speciation. Future objectives discussed include improved means of communicating speciation-based recommendations to decision makers. PMID:18365083

Selenium speciation in acidic environmental samples: application to acid rain-soil interaction at Mount Etna volcano.

PubMed

Floor, Geerke H; Iglesías, Mònica; Román-Ross, Gabriela; Corvini, Philippe F X; Lenz, Markus

2011-09-01

Speciation plays a crucial role in elemental mobility. However, trace level selenium (Se) speciation analyses in aqueous samples from acidic environments are hampered due to adsorption of the analytes (i.e. selenate, selenite) on precipitates. Such solid phases can form during pH adaptation up till now necessary for chromatographic separation. Thermodynamic calculations in this study predicted that a pH<4 is needed to prevent precipitation of Al and Fe phases. Therefore, a speciation method with a low pH eluent that matches the natural sample pH of acid rain-soil interaction samples from Etna volcano was developed. With a mobile phase containing 20mM ammonium citrate at pH 3, selenate and selenite could be separated in different acidic media (spiked water, rain, soil leachates) in <10 min with a LOQ of 0.2 μg L(-1) using (78)Se for detection. Applying this speciation analysis to study acid rain-soil interaction using synthetic rain based on H(2)SO(4) and soil samples collected at the flanks of Etna volcano demonstrated the dominance of selenate over selenite in leachates from samples collected close to the volcanic craters. This suggests that competitive behavior with sulfate present in acid rain might be a key factor in Se mobilization. The developed speciation method can significantly contribute to understand Se cycling in acidic, Al/Fe rich environments. Copyright © 2011 Elsevier Ltd. All rights reserved.

Recent Advances in the Measurement of Arsenic, Cadmium, and Mercury in Rice and Other Foods

PubMed Central

Punshon, Tracy

2015-01-01

Trace element analysis of foods is of increasing importance because of raised consumer awareness and the need to evaluate and establish regulatory guidelines for toxic trace metals and metalloids. This paper reviews recent advances in the analysis of trace elements in food, including challenges, state-of-the art methods, and use of spatially resolved techniques for localizing the distribution of As and Hg within rice grains. Total elemental analysis of foods is relatively well-established but the push for ever lower detection limits requires that methods be robust from potential matrix interferences which can be particularly severe for food. Inductively coupled plasma mass spectrometry (ICP-MS) is the method of choice, allowing for multi-element and highly sensitive analyses. For arsenic, speciation analysis is necessary because the inorganic forms are more likely to be subject to regulatory limits. Chromatographic techniques coupled to ICP-MS are most often used for arsenic speciation and a range of methods now exist for a variety of different arsenic species in different food matrices. Speciation and spatial analysis of foods, especially rice, can also be achieved with synchrotron techniques. Sensitive analytical techniques and methodological advances provide robust methods for the assessment of several metals in animal and plant-based foods, in particular for arsenic, cadmium and mercury in rice and arsenic speciation in foodstuffs. PMID:25938012

Application of Hyphenated Techniques in Speciation Analysis of Arsenic, Antimony, and Thallium

PubMed Central

Michalski, Rajmund; Szopa, Sebastian; Jabłońska, Magdalena; Łyko, Aleksandra

2012-01-01

Due to the fact that metals and metalloids have a strong impact on the environment, the methods of their determination and speciation have received special attention in recent years. Arsenic, antimony, and thallium are important examples of such toxic elements. Their speciation is especially important in the environmental and biomedical fields because of their toxicity, bioavailability, and reactivity. Recently, speciation analytics has been playing a unique role in the studies of biogeochemical cycles of chemical compounds, determination of toxicity and ecotoxicity of selected elements, quality control of food products, control of medicines and pharmaceutical products, technological process control, research on the impact of technological installation on the environment, examination of occupational exposure, and clinical analysis. Conventional methods are usually labor intensive, time consuming, and susceptible to interferences. The hyphenated techniques, in which separation method is coupled with multidimensional detectors, have become useful alternatives. The main advantages of those techniques consist in extremely low detection and quantification limits, insignificant interference, influence as well as high precision and repeatability of the determinations. In view of their importance, the present work overviews and discusses different hyphenated techniques used for arsenic, antimony, and thallium species analysis, in different clinical, environmental and food matrices. PMID:22654649

THE DISTRIBUTION, SOLID-PHASE SPECIATION, AND DESORPTION/DISSOLUTION OF AS IN IRON-BASED DRINKING WATER TREATMENT MEDIA 1

EPA Science Inventory

Arsenic concentrations (Total Recoverable As by EPA Method 3051, soluble, Toxicity Characteristic Leaching Procedure extractable) and solid-phase speciation (by X-ray Absorption Near-Edge Spectroscopy-XANES) were assessed as a function of depth through Fe-media beds for two comme...

Selenium speciation analysis of Misgurnus anguillicaudatus selenoprotein by HPLC-ICP-MS and HPLC-ESI-MS/MS

USDA-ARS?s Scientific Manuscript database

Analytical methods for selenium (Se) speciation were developed using high performance liquid chromatography (HPLC) coupled to either inductively coupled plasma mass spectrometry (ICP-MS) or electrospray ionization tandem mass spectrometry (ESI-MS/MS). Separations of selenomethionine (Se-Met) and sel...

THE DISTRIBUTION, SOLID-PHASE SPECIATION, AND DESORPTION/DISSOLUTION OF AS IN IRON-BASED TREATMENT MEDIA

EPA Science Inventory

Arsenic concentrations (Total Recoverable As by EPA Method 3051) and solid-phase speciation (by X-ray Absorption Near-Edge Spectroscopy-XANES) were assessed as a function of depth through Fe-media beds for two commercially available products from pilot-scale field tests. These re...

THE DISTRIBUTION, SOLID-PHASE SPECIATION, AND DESORPTION/DISSOLUTION OF AS IN IRON-BASED DRINKING WATER TREATMENT MEDIA - JOURNAL

EPA Science Inventory

Arsenic concentrations (Total Recoverable As by EPA Method 3051, soluble, Toxicity Characteristic Leaching Procedure extractable) and solid-phase speciation (by X-ray Absorption Near-Edge Spectroscopy-XANES) were assessed as a function of depth through Fe-media beds for two comme...

THE DISTRIBUTION AND SOLID-PHASE SPECIATION OF AS IN IRON-BASED TREATMENT MEDIA

EPA Science Inventory

Arsenic concentrations (Total Recoverable As by EPA Method 3051) and solid-phase speciation (by X-ray Absorption Near-Edge Spectroscopy-XANES) were assessed as a function of depth through Fe-media beds for two commercially available products from pilot-scale field tests. These r...

METHODS INTERCOMPARISON OF SAMPLERS FOR EPA'S NATIONAL PM 2.5 CHEMICAL SPECIATION NETWORK

EPA Science Inventory

The objective of this sampler intercomparison field study is to determine the performance characteristics for the collection of the chemical components of PM2.5 by the chemical speciation monitors developed for the national PM2.5 network relative to each other, to the Federal R...

Speciation of heavy metals in landfill leachate: a review.

PubMed

Baun, Dorthe L; Christensen, Thomas H

2004-02-01

The literature was reviewed with respect to metal speciation methods in aquatic samples specifically emphasizing speciation of heavy metals in landfill leachate. Speciation here refers to physical fractionation (particulate, colloidal, dissolved), chemical fractionation (organic complexes, inorganic complexes, free metal ions), as well as computer-based thermodynamic models. Relatively few landfill leachate samples have been speciated in detail (less than 30) representing only a few landfills (less than 15). This suggests that our knowledge about metal species in landfill leachate still is indicative. In spite of the limited database and the different definitions of the dissolved fraction (< 0.45 microm or < 0.001 microm) the studies consistently show that colloids as well as organic and inorganic complexes are important for all heavy metals in landfill leachate. The free metal ion constitutes less than 30%, typically less than 10%, of the total metal concentration. This has significant implications for sampling, since no standardized procedures exist, and for assessing the content of metals in leachate in the context of its treatment, toxicity and migration in aquifers.

In Vitro Model To Assess Arsenic Bioaccessibility and Speciation in Cooked Shrimp.

PubMed

Chi, Haifeng; Zhang, Youchi; Williams, Paul N; Lin, Shanna; Hou, Yanwei; Cai, Chao

2018-05-09

Shrimp, a popular and readily consumed seafood, contains high concentrations of arsenic. However, few studies have focused on whether arsenic in the shrimp could be transformed during the cooking process and gastrointestinal digestion. In this study, a combined in vitro model [Unified Bioaccessibility Research Group of Europe (BARGE) Method-Simulator of Human Intestinal Microbial Ecosystem (UBM-SHIME)] was used to investigate arsenic bioaccessibility and its speciation in raw and cooked shrimps. The results showed that the cooking practices had little effect on the arsenic content and speciation. Bioaccessibility of arsenic in raw shrimp was at a high level, averaging 76.9 ± 4.28 and 86.7 ± 3.74% in gastric and small intestinal phases, respectively. Arsenic speciation was stable in all of the shrimp digestions, with nontoxic arsenobetaine (AsB) being the dominated speciation. The cooking practice significantly increased the bioaccessibility of arsenate ( p < 0.05) in shrimp digests, indicating the increase of the potential health risks.

Arsenic, Antimony, Chromium, and Thallium Speciation in Water and Sediment Samples with the LC-ICP-MS Technique

PubMed Central

Jabłońska-Czapla, Magdalena

2015-01-01

Chemical speciation is a very important subject in the environmental protection, toxicology, and chemical analytics due to the fact that toxicity, availability, and reactivity of trace elements depend on the chemical forms in which these elements occur. Research on low analyte levels, particularly in complex matrix samples, requires more and more advanced and sophisticated analytical methods and techniques. The latest trends in this field concern the so-called hyphenated techniques. Arsenic, antimony, chromium, and (underestimated) thallium attract the closest attention of toxicologists and analysts. The properties of those elements depend on the oxidation state in which they occur. The aim of the following paper is to answer the question why the speciation analytics is so important. The paper also provides numerous examples of the hyphenated technique usage (e.g., the LC-ICP-MS application in the speciation analysis of chromium, antimony, arsenic, or thallium in water and bottom sediment samples). An important issue addressed is the preparation of environmental samples for speciation analysis. PMID:25873962

Analytical methodologies for aluminium speciation in environmental and biological samples--a review.

PubMed

Bi, S P; Yang, X D; Zhang, F P; Wang, X L; Zou, G W

2001-08-01

It is recognized that aluminium (Al) is a potential environmental hazard. Acidic deposition has been linked to increased Al concentrations in natural waters. Elevated levels of Al might have serious consequences for biological communities. Of particular interest is the speciation of Al in aquatic environments, because Al toxicity depends on its forms and concentrations. In this paper, advances in analytical methodologies for Al speciation in environmental and biological samples during the past five years are reviewed. Concerns about the specific problems of Al speciation and highlights of some important methods are elucidated in sections devoted to hybrid techniques (HPLC or FPLC coupled with ET-AAS, ICP-AES, or ICP-MS), flow-injection analysis (FIA), nuclear magnetic resonance (27Al NMR), electrochemical analysis, and computer simulation. More than 130 references are cited.

High-Iron Biosolids Compost-Induced Changes in Lead and Arsenic Speciation and Bioaccessibility in Co-contaminated Soils

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brown, Sally L; Clausen, Ingrid; Chappell, Mark A

2012-10-23

The safety of urban farming has been questioned due to the potential for contamination in urban soils. A laboratory incubation, a field trial, and a second laboratory incubation were conducted to test the ability of high-Fe biosolids–based composts to reduce the bioaccessibility of soil Pb and As in situ. Lead and As bioaccessibility were evaluated using an in vitro assay. Changes in Pb, As, and Fe speciation were determined on select samples after the second laboratory incubation using μ–X-ray fluorescence mapping followed by μ–X-ray absorption near-edge structure (XANES). A compost with Fe added to wastewater treatment residuals (Fe WTR compost)more » added to soils at 100 g kg -1 decreased Pb bioaccessibility in both laboratory incubations. Mixed results were observed for As. Composts tested in the field trial (Fe added as Fe powder or FeCl 2) did not reduce bioaccessible Pb, and limited reductions were observed in bioaccessible As. These composts had no effect on Pb bioaccessibility during the second laboratory incubation. Bulk XANES showed association of Pb with sulfates and carbonates in the control soil. μ-XANES for three points in the Fe WTR amended soil showed Pb present as Fe-sorbed Pb (88 and 100% of two points) and pyromorphite (12 and 53% of two points). Bulk XANES of the Fe WTR compost showed 97% of total Fe present as Fe 3+. The results of this study indicate that addition of high-Fe biosolids compost is an effective means to reduce Pb accessibility only for certain types of Fe-rich materials.« less

Nickel and manganese transfer from soil to plant in lateritic mining soils from New Caledonia

NASA Astrophysics Data System (ADS)

Pouschat, P.; Rose, J.; Alliot, I.; Dominici, C.; Keller, C.; Laffont-Schwob, I.; Olivi, L.; Ambrosi, J.-P.

2009-04-01

New Caledonian ferritic soils (more than 50 % of iron) are naturally rich in metals (chromium, nickel, cobalt, and manganese), deficient in major nutrients (nitrogen, phosphorous, and potassium), and unbalanced for the calcium/magnesium ratio. Under these particular ecological conditions, New Caledonia, recognized as a hot-spot of biodiversity, is a natural laboratory to study and understand the adaptation strategies of plants to metalliferous soils, and particularly the tolerance and (hyper)accumulation of metals by plants. Moreover, understanding such mechanisms is essential to develop rehabilitation or phytoremediation techniques for polluted soils, as well as phytomining techniques. Thus, in order to understand the soil - plant relationship and metal mobility along a toposequence in a future nickel mining massif, field experiments were conducted in an isolated ultramafic massif of New Caledonia. Several plant species of two endemic and frequent plant genera were chosen: Tristaniopsis guillainii and T. calobuxus (Myrtaceae), and Phyllanthus serpentinus and P. favieri (Euphorbiaceae), because of their nickel and/or manganese accumulating or hyperaccumulating nature. Leaves, twigs, and roots of all plants were collected along the soil sequence and their associated rhizospheric and bulk soils were sampled. Next, a series of characterization techniques were adapted and then coupled to cryogenics. The combined use of those multiple techniques (cryo-microtomy, cryo-SEM, µXRF, cryo-XAS, and soil characterization) allowed to study co-location and speciation of nickel and manganese in the different plant organs and soils (rhizospheric and bulk). Bioaccumulated nickel and manganese had different distribution patterns. In leaves, Ni accumulated in non photosynthetic tissues (e.g. epidermis) whereas Mn preferentially accumulated in mesophyll whatever the plant species. Nevertheless, in spite of a different speciation in soils, nickel and manganese were both found as similar divalent organometallic complexes in the different plant parts.

Volcanic gas composition, metal dispersion and deposition during explosive volcanic eruptions on the Moon

NASA Astrophysics Data System (ADS)

Renggli, C. J.; King, P. L.; Henley, R. W.; Norman, M. D.

2017-06-01

The transport of metals in volcanic gases on the Moon differs greatly from their transport on the Earth because metal speciation depends largely on gas composition, temperature, pressure and oxidation state. We present a new thermochemical model for the major and trace element composition of lunar volcanic gas during pyroclastic eruptions of picritic magmas calculated at 200-1500 °C and over 10-9-103 bar. Using published volatile component concentrations in picritic lunar glasses, we have calculated the speciation of major elements (H, O, C, Cl, S and F) in the coexisting volcanic gas as the eruption proceeds. The most abundant gases are CO, H2, H2S, COS and S2, with a transition from predominantly triatomic gases to diatomic gases with increasing temperatures and decreasing pressures. Hydrogen occurs as H2, H2S, H2S2, HCl, and HF, with H2 making up 0.5-0.8 mol fractions of the total H. Water (H2O) concentrations are at trace levels, which implies that H-species other than H2O need to be considered in lunar melts and estimates of the bulk lunar composition. The Cl and S contents of the gas control metal chloride gas species, and sulfide gas and precipitated solid species. We calculate the speciation of trace metals (Zn, Ga, Cu, Pb, Ni, Fe) in the gas phase, and also the pressure and temperature conditions at which solids form from the gas. During initial stages of the eruption, elemental gases are the dominant metal species. As the gas loses heat, chloride and sulfide species become more abundant. Our chemical speciation model is applied to a lunar pyroclastic eruption model with isentropic gas decompression. The relative abundances of the deposited metal-bearing solids with distance from the vent are predicted for slow cooling rates (<5 °C/s). Close to a volcanic vent we predict native metals are deposited, whereas metal sulfides dominate with increasing distance from the vent. Finally, the lunar gas speciation model is compared with the speciation of a H2O-, CO2- and Cl-rich volcanic gas from Erta Ale volcano (Ethiopia) as an analogy for more oxidized planetary eruptions. In the terrestrial Cl-rich gas the metals are predominantly transported as chlorides, as opposed to metallic vapors and sulfides in the lunar gas. Due to the presence of Cl-species, metal transport is more efficient in the volcanic gas from Erta Ale compared to the Moon.

Presumptive speciation of Streptococcus bovis and other group D streptococci from human sources by using arginine and pyruvate tests.

PubMed Central

Gross, K C; Houghton, M P; Senterfit, L B

1975-01-01

A simplified method for speciation of group D streptococci is described. A total of 4,156 streptococcal isolates from human clinical material was tested for ability to hydrolyze esculin in the presence of 40% bile, ferment pyruvate, hydrolyze arginine, and grow in media containing 40% bile or 6.5% NaCl. Streptococci which hydrolyzed esculin in 40% bile, but which did not hydrolyze arginine, were also tested for their ability to ferment raffinose or sorbose. Sixty percent (2,503) of the isolates hydrolyzed esculin in the presence of 40% bile and were thus presumptively identified as group D. By application of the other criteria, 84% of these were speciated as Streptococcus faecalis, 7% were speciated as S. faecium, 6% were speciated as S. bovis, 2% were speciated as S. avium, and 1% were not identified. This scheme was shown to be both reliable and practical for use in the diagnostic laboratory. S. avium and S. bovis isolates were characterized, and 18 S. bovis isolates from patients with bacterial endocarditis were compared physiologically with 151 isolates of this species from other sources. PMID:1176592

Quantitative traits and diversification.

PubMed

FitzJohn, Richard G

2010-12-01

Quantitative traits have long been hypothesized to affect speciation and extinction rates. For example, smaller body size or increased specialization may be associated with increased rates of diversification. Here, I present a phylogenetic likelihood-based method (quantitative state speciation and extinction [QuaSSE]) that can be used to test such hypotheses using extant character distributions. This approach assumes that diversification follows a birth-death process where speciation and extinction rates may vary with one or more traits that evolve under a diffusion model. Speciation and extinction rates may be arbitrary functions of the character state, allowing much flexibility in testing models of trait-dependent diversification. I test the approach using simulated phylogenies and show that a known relationship between speciation and a quantitative character could be recovered in up to 80% of the cases on large trees (500 species). Consistent with other approaches, detecting shifts in diversification due to differences in extinction rates was harder than when due to differences in speciation rates. Finally, I demonstrate the application of QuaSSE to investigate the correlation between body size and diversification in primates, concluding that clade-specific differences in diversification may be more important than size-dependent diversification in shaping the patterns of diversity within this group.

Solid phase extraction for the speciation and preconcentration of inorganic selenium in water samples: a review.

PubMed

Herrero Latorre, C; Barciela García, J; García Martín, S; Peña Crecente, R M

2013-12-04

Selenium is an essential element for the normal cellular function of living organisms. However, selenium is toxic at concentrations of only three to five times higher than the essential concentration. The inorganic forms (mainly selenite and selenate) present in environmental water generally exhibit higher toxicity (up to 40 times) than organic forms. Therefore, the determination of low levels of different inorganic selenium species in water is an analytical challenge. Solid-phase extraction has been used as a separation and/or preconcentration technique prior to the determination of selenium species due to the need for accurate measurements for Se species in water at extremely low levels. The present paper provides a critical review of the published methods for inorganic selenium speciation in water samples using solid phase extraction as a preconcentration procedure. On the basis of more than 75 references, the different speciation strategies used for this task have been highlighted and classified. The solid-phase extraction sorbents and the performance and analytical characteristics of the developed methods for Se speciation are also discussed. Copyright © 2013 Elsevier B.V. All rights reserved.

Testing the role of climate in speciation: new methods and applications to squamate reptiles (lizards and snakes).

PubMed

Jezkova, Tereza; Wiens, John J

2018-05-19

Climate may play important roles in speciation, such as causing the range fragmentation that underlies allopatric speciation (through niche conservatism) or driving divergence of parapatric populations along climatic gradients (through niche divergence). Here, we developed new methods to test the frequency of climate niche conservatism and divergence in speciation, and applied it to species pairs of squamate reptiles (lizards and snakes). We used a large-scale phylogeny to identify 242 sister-species pairs for analysis. From these, we selected all terrestrial allopatric pairs with sufficient occurrence records (n=49 pairs) and inferred whether each originated via climatic niche conservatism or climatic niche divergence. Among the 242 pairs, allopatric pairs were most common (41.3%), rather than parapatric (19.4%), partially sympatric (17.7%), or fully sympatric species pairs (21.5%). Among the 49 selected allopatric pairs, most appeared to have originated via climatic niche divergence (61-76%, depending on the details of the methods). Surprisingly, we found greater climatic niche divergence between allopatric sister species than between parapatric pairs, even after correcting for geographic distance. We also found that niche divergence did not increase with time, further implicating niche divergence in driving lineage splitting. Overall, our results suggest that climatic niche divergence may often play an important role in allopatric speciation, and the methodology developed here can be used to address the generality of these findings in other organisms. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

Surfactant-assisted emulsification dispersive liquid-liquid microextraction using 2-thenoyltrifluoroacetone as a chelating agent coupled with electrothermal atomic absorption spectrometry for the speciation of chromium in water and rice samples.

PubMed

Dokpikul, Nattawut; Chaiyasith, Wipharat Chuachuad; Sananmuang, Ratana; Ampiah-Bonney, Richmond J

2018-04-25

A novel method was developed by SAE-DLLME for chromium speciation in water and rice samples using 2-thenoyltrifluoroacetone (TTA) as a chelating reagent by ETAAS. The speciation of Cr(III) and Cr(VI) was achieved by complexation of Cr(III)-TTA and the total Cr was measured after reduction of Cr(VI) to Cr. The calibration graph was linear in the range of 0.02-2.50 µg L -1 , with a detection limit of 0.0052 µg L -1 . The %RSD was in range of 2.90-3.30% at 0.5, 1.5 and 2.5 µg L -1 of Cr(III), n = 5 and the EF was 54.47. The method was applied to chromium speciation and total chromium determination in real samples and gave recoveries in the range of 96.2-103.5% and 97.1-102.7% for Cr(III) and Cr(VI) in water samples and 93.7-103.5% of total Cr in rice samples. The accuracy of the method was evaluated by analysis of SRM 1573a with good agreement compared to the certified value. Copyright © 2017 Elsevier Ltd. All rights reserved.

Uranium speciation as a function of depth in contaminated hanford sediments--a micro-XRF, micro-XRD, and micro- and bulk-XAFS study.

PubMed

Singer, David M; Zachara, John M; Brown, Gordon E

2009-02-01

The distribution and speciation of U and Cu in contaminated vadose zone and aquifer sediments from the U.S. DOE Hanford site (300 Area) were determined using a combination of synchrotron-based micro-X-ray fluorescence (microXRF) imaging, micro-X-ray absorption near edge structure (microXANES) spectroscopy, and micro-X-ray diffraction (microXRD) techniques combined with bulk U LIII-edge X-ray absorption fine structure (XAFS) spectroscopy. Samples were collected from within the inactive North Process Pond (NPP2) at 8 ft (2.4 m, NPP2-8) depth and 12 ft (3.7 m, NPP2-12) depth in the vadose zone, and fines were isolated from turbid groundwater just below the water Table (12-14 ft, approximately 4 m, NPP2-GW). microXRF imaging, microXRD, and microXANES spectroscopy revealed two major U occurrences within the vadose and groundwater zones: (1) low to moderate concentrations of U(VI) associated with fine-textured grain coatings that were consistently found to contain clinochlore (referred to here as chlorite) observed in all three samples, and (2) U(VI)-Cu(II) hotspots consisting of micrometer-sized particles associated with surface coatings on grains of muscovite and chlorite observed in samples NPP2-8' and NPP2-GW. In the aquifer fines (NPP2-GW), these particles were identified as cuprosklodowskite (cps: Cu[(UO2)(SiO2OH)]2 x 6H2O) and metatorbernite (mtb: Cu(UO2)2(PO4)2 x 8H2O). In contrast, the U-Cu-containing particles in the vadose zone were X-ray amorphous. Analyses of U LIII-edge XAFS spectra by linear-combination fitting indicated that U speciation consisted of (1) approximately 75% uranyl sorbed to chlorite and approximately 25% mtb-like X-ray amorphous U-Cu-phosphates (8 ft depth), (2) nearly 100% sorbed uranyl (12 ft depth), and (3) approximately 70% uranyl sorbed to chlorite and approximately 30% cps/mtb (groundwater zone). These findings suggest that dissolution of U(VI)-Cu(II)-bearing solids as well as desorption of U(VI), mainly from phyllosilicates, are important persistent sources of U(VI) to the associated uranium groundwater plume in Hanford Area 300.

Layer speciation and electronic structure investigation of freestanding hexagonal boron nitride nanosheets

NASA Astrophysics Data System (ADS)

WangEqual Contribution To This Work., Jian; Wang, Zhiqiang; Cho, Hyunjin; Kim, Myung Jong; Sham, T. K.; Sun, Xuhui

2015-01-01

Chemical imaging, thickness mapping, layer speciation and polarization dependence have been performed on single and multilayered (up to three layers and trilayered nanosheets overlapping to form 6 and 9 layers) hexagonal boron nitride (hBN) nanosheets by scanning transmission X-ray microscopy. Spatially-resolved XANES directly from freestanding regions of different layers has been extracted and compared with sample normal and 30° tilted configurations. Notably a double feature σ* excitonic state and a stable high energy σ* state were observed at the boron site in addition to the intense π* excitonic state. The boron projected σ* DOS, especially the first σ* exciton, is sensitive to surface modification, particularly in the single layered hBN nanosheet which shows more significant detectable contaminants and defects such as tri-coordinated boron/nitrogen oxide. The nitrogen site has shown very weak or no excitonic character. The distinct excitonic effect on boron and nitrogen was interpreted to the partly ionic state of hBN. Bulk XANES of hBN nanosheets was also measured to confirm the spectro-microscopic STXM result. Finally, the unoccupied electronic structures of hBN and graphene were compared.Chemical imaging, thickness mapping, layer speciation and polarization dependence have been performed on single and multilayered (up to three layers and trilayered nanosheets overlapping to form 6 and 9 layers) hexagonal boron nitride (hBN) nanosheets by scanning transmission X-ray microscopy. Spatially-resolved XANES directly from freestanding regions of different layers has been extracted and compared with sample normal and 30° tilted configurations. Notably a double feature σ* excitonic state and a stable high energy σ* state were observed at the boron site in addition to the intense π* excitonic state. The boron projected σ* DOS, especially the first σ* exciton, is sensitive to surface modification, particularly in the single layered hBN nanosheet which shows more significant detectable contaminants and defects such as tri-coordinated boron/nitrogen oxide. The nitrogen site has shown very weak or no excitonic character. The distinct excitonic effect on boron and nitrogen was interpreted to the partly ionic state of hBN. Bulk XANES of hBN nanosheets was also measured to confirm the spectro-microscopic STXM result. Finally, the unoccupied electronic structures of hBN and graphene were compared. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr04445b

Lead speciation in indoor dust: a case study to assess old paint contribution in a Canadian urban house

DOE Office of Scientific and Technical Information (OSTI.GOV)

Beauchemin, Suzanne; MacLean, Lachlan C.W.; Rasmussen, Pat E.

Residents in older homes may experience increased lead (Pb) exposures due to release of lead from interior paints manufactured in past decades, especially pre-1960s. The objective of the study was to determine the speciation of Pb in settled dust from an urban home built during WWII. X-ray absorption near-edge structure (XANES) and micro-X-ray diffraction (XRD) analyses were performed on samples of paint (380-2,920 mg Pb kg{sup -1}) and dust (200-1,000 mg Pb kg{sup -1}) collected prior to renovation. All dust samples exhibited a Pb XANES signature similar to that of Pb found in paint. Bulk XANES and micro-XRD identified Pbmore » species commonly found as white paint pigments (Pb oxide, Pb sulfate, and Pb carbonate) as well as rutile, a titanium-based pigment, in the <150 {micro}m house dust samples. In the dust fraction <36 {micro}m, half of the Pb was associated with the Fe-oxyhydroxides, suggesting additional contribution of outdoor sources to Pb in the finer dust. These results confirm that old paints still contribute to Pb in the settled dust for this 65-year-old home. The Pb speciation also provided a clearer understanding of the Pb bioaccessibility: Pb carbonate > Pb oxide > Pb sulfate. This study underscores the importance of taking precautions to minimize exposures to Pb in house dust, especially in homes where old paint is exposed due to renovations or deterioration of painted surfaces.« less

Lead Speciation in Indoor Dust: A Case Study to Assess Old Paint Contribution in a Canadian Urban House

DOE Office of Scientific and Technical Information (OSTI.GOV)

S Beauchemin; L MacLean; P Rasmussen

Residents in older homes may experience increased lead (Pb) exposures due to release of lead from interior paints manufactured in past decades, especially pre-1960s. The objective of the study was to determine the speciation of Pb in settled dust from an urban home built during WWII. X-ray absorption near-edge structure (XANES) and micro-X-ray diffraction (XRD) analyses were performed on samples of paint (380-2,920 mg Pb kg{sup -1}) and dust (200-1,000 mg Pb kg{sup -1}) collected prior to renovation. All dust samples exhibited a Pb XANES signature similar to that of Pb found in paint. Bulk XANES and micro-XRD identified Pbmore » species commonly found as white paint pigments (Pb oxide, Pb sulfate, and Pb carbonate) as well as rutile, a titanium-based pigment, in the <150 m house dust samples. In the dust fraction <36 {mu}m, half of the Pb was associated with the Fe-oxyhydroxides, suggesting additional contribution of outdoor sources to Pb in the finer dust. These results confirm that old paints still contribute to Pb in the settled dust for this 65-year-old home. The Pb speciation also provided a clearer understanding of the Pb bioaccessibility: Pb carbonate > Pb oxide > Pb sulfate. This study underscores the importance of taking precautions to minimize exposures to Pb in house dust, especially in homes where old paint is exposed due to renovations or deterioration of painted surfaces.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dublet, Gabrielle; Juillot, Farid; Brest, Jessica

Because they can host significant amounts of Co, the Mn-oxides are commonly considered as the major Co-bearing mineral species in lateritic environments. However, little is known about the process leading to the formation and/or the weathering of these Co-rich Mn-oxides. This lack of knowledge is mainly due to the fact that Co concentrations are too low in primary silicates for classical speciation analysis. In this study, we investigated both Co and Mn speciation in a 64 m thick lateritic regolith developed upon peridotites in New Caledonia, by combining High Energy Resolution Fluorescence Detection X-ray absorption Near Edge Structure (HERFD-XANES) spectroscopymore » at the Co K-edge with classical XANES spectroscopy at the Mn K-edge, bulk chemistry (ICP) and mineralogy (XRD). The results obtained provide new insights into the evolution of Co and Mn speciation as a function of the weathering stages. Co and Mn primarily occur as Co(II) and Mn(II,III) in olivine and serpentine in the bedrock. During the first weathering stage, these forms of Co and Mn are progressively oxidized toward Co(III) and Mn(III,IV), which occur mainly as Co(III)-bearing Mn(III/IV)-oxides in the transition between the saprolite and the laterite. In the uppermost lateritic horizons, long-time weathering resulted in a strong leaching of Co and Mn, and the remaining of these elements occurs as Co(II) and Mn(III) substituting for Fe(III) in goethite. Finally, this latter scavenging process emphasizes the importance of Fe-oxides for the long-term stabilization of Co and Mn in such deeply weathered laterites.« less

Source-term characterisation and solid speciation of plutonium at the Semipalatinsk NTS, Kazakhstan.

PubMed

Nápoles, H Jiménez; León Vintró, L; Mitchell, P I; Omarova, A; Burkitbayev, M; Priest, N D; Artemyev, O; Lukashenko, S

2004-01-01

New data on the concentrations of key fission/activation products and transuranium nuclides in samples of soil and water from the Semipalatinsk Nuclear Test Site are presented and interpreted. Sampling was carried out at Ground Zero, Lake Balapan, the Tel'kem craters and reference locations within the test site boundary well removed from localised sources. Radionuclide ratios have been used to characterise the source term(s) at each of these sites. The geochemical partitioning of plutonium has also been examined and it is shown that the bulk of the plutonium contamination at most of the sites examined is in a highly refractory, non-labile form.

Time-dependent changes of zinc speciation in four soils contaminated with zincite or sphalerite.

PubMed

Voegelin, Andreas; Jacquat, Olivier; Pfister, Sabina; Barmettler, Kurt; Scheinost, Andreas C; Kretzschmar, Ruben

2011-01-01

The long-term speciation of Zn in contaminated soils is strongly influenced by soil pH, clay, and organic matter content as well as Zn loading. In addition, the type of Zn-bearing contaminant entering the soil may influence the subsequent formation of pedogenic Zn species, but systematic studies on such effects are currently lacking. We therefore conducted a soil incubation study in which four soils, ranging from strongly acidic to calcareous, were spiked with 2000 mg/kg Zn using either ZnO (zincite) or ZnS (sphalerite) as the contamination source. The soils were incubated under aerated conditions in moist state for up to four years. The extractability and speciation of Zn were assessed after one, two, and four years using extractions with 0.01 M CaCl(2) and Zn K-edge X-ray absorption fine structure (XAFS) spectroscopy, respectively. After four years, more than 90% of the added ZnO were dissolved in all soils, with the fastest dissolution occurring in the acidic soils. Contamination with ZnO favored the formation of Zn-bearing layered double hydroxides (LDH), even in acidic soils, and to a lesser degree Zn-phyllosilicates and adsorbed Zn species. This was explained by locally elevated pH and high Zn concentrations around dissolving ZnO particles. Except for the calcareous soil, ZnS dissolved more slowly than ZnO, reaching only 26 to 75% of the added ZnS after four years. ZnS dissolved more slowly in the two acidic soils than in the near-neutral and the calcareous soil. Also, the resulting Zn speciation was markedly different between these two pairs of soils: Whereas Zn bound to hydroxy-interlayered clay minerals (HIM) and octahedrally coordinated Zn sorption complexes prevailed in the two acidic soils, Zn speciation in the neutral and the calcareous soil was dominated by Zn-LDH and tetrahedrally coordinated inner-sphere Zn complexes. Our results show that the type of Zn-bearing contaminant phase can have a significant influence on the formation of pedogenic Zn species in soils. Important factors include the rate of Zn release from the contaminant phases and effects of the contaminant phase on bulk soil properties and on local chemical conditions around weathering contaminant particles.

Particle-size dependence on metal(loid) distributions in mine wastes: Implications for water contamination and human exposure

USGS Publications Warehouse

Kim, C.S.; Wilson, K.M.; Rytuba, J.J.

2011-01-01

The mining and processing of metal-bearing ores has resulted in contamination issues where waste materials from abandoned mines remain in piles of untreated and unconsolidated material, posing the potential for waterborne and airborne transport of toxic elements. This study presents a systematic method of particle size separation, mass distribution, and bulk chemical analysis for mine tailings and adjacent background soil samples from the Rand historic mining district, California, in order to assess particle size distribution and related trends in metal(loid) concentration as a function of particle size. Mine tailings produced through stamp milling and leaching processes were found to have both a narrower and finer particle size distribution than background samples, with significant fractions of particles available in a size range (???250 ??m) that could be incidentally ingested. In both tailings and background samples, the majority of trace metal(loid)s display an inverse relationship between concentration and particle size, resulting in higher proportions of As, Cr, Cu, Pb and Zn in finer-sized fractions which are more susceptible to both water- and wind-borne transport as well as ingestion and/or inhalation. Established regulatory screening levels for such elements may, therefore, significantly underestimate potential exposure risk if relying solely on bulk sample concentrations to guide remediation decisions. Correlations in elemental concentration trends (such as between As and Fe) indicate relationships between elements that may be relevant to their chemical speciation. ?? 2011 Elsevier Ltd.

Application of ESI-HRMS for molybdenum speciation in natural waters: An investigation of molybdate-halide reactions.

PubMed

Dang, Duc Huy; Evans, R Douglas

2018-03-01

High resolution electrospray ionization mass spectrometry (ESI-HRMS) was used to study the speciation of molybdate in interaction with halides (Cl, F, Br). Desolvation during electrospray ionization induced alteration of aqueous species but method optimization successfully suppressed artefact compounds. At low Mo concentrations, chloro(oxo)molybdate and fluoro(oxo)molybdate species were found and in natural samples, MoO 3 Cl was detected for the first time, to the best of our knowledge. Apparent equilibrium constants for Cl substitution on molybdate were calculated for a range of pH values from 4.5 to 8.5. A minor alteration in speciation during the gas phase (conversion of doubly charged MoO 4 2- to HMoO 4 - ) did not allow investigation of the molybdate acid-base properties; however this could be determined by speciation modeling. This study provides further evidence that ESI-HRMS is a fast and suitable tool to Deceasedassess the speciation of inorganic compounds such as Mo. Copyright © 2017 Elsevier B.V. All rights reserved.

Habitat and Burrow System Characteristics of the Blind Mole Rat Spalax galili in an Area of Supposed Sympatric Speciation

PubMed Central

Lövy, Matěj; Šklíba, Jan; Hrouzková, Ema; Dvořáková, Veronika; Nevo, Eviatar; Šumbera, Radim

2015-01-01

A costly search for food in subterranean rodents resulted in various adaptations improving their foraging success under given ecological conditions. In Spalax ehrenbergi superspecies, adaptations to local ecological conditions can promote speciation, which was recently supposed to occur even in sympatry at sites where two soil types of contrasting characteristics abut each other. Quantitative description of ecological conditions in such a site has been, nevertheless, missing. We measured characteristics of food supply and soil within 16 home ranges of blind mole rats Spalax galili in an area subdivided into two parts formed by basaltic soil and pale rendzina. We also mapped nine complete mole rat burrow systems to compare burrowing patterns between the soil types. Basaltic soil had a higher food supply and was harder than rendzina even under higher moisture content and lower bulk density. Population density of mole rats was five-times lower in rendzina, possibly due to the lower food supply and higher cover of Sarcopoterium shrubs which seem to be avoided by mole rats. A combination of food supply and soil parameters probably influences burrowing patterns resulting in shorter and more complex burrow systems in basaltic soil. PMID:26192762

Barcode index number, taxonomic rank and modes of speciation: examples from fish.

PubMed

Kartavtsev, Yuri Phedorovich

2018-05-01

Species delimitation by DNA sequence data or DNA barcoding is successful, as confirmed by the vast BOLD data base. However, the theory that would explain this fact has not been developed yet. An approach based on Barcoding Index Number (BIN), suggested in the assignment, allows delimiting of taxa of three ranks (species, genera, and families) and statistical validation with a high precision of delimiting (over 80%), as well as shows for majority of Co-1-based single gene trees good correspondence between their topology and conventional taxa content for analyzed fish species (R 2  ≈ 0.84-0.98). Knowledge of deviations from these data can help to find out new taxa and improve biodiversity description. It is concluded that delimiting is successful for bulk of cases because the geographic mode of speciation prevails in nature. It takes a long time for new taxa to form in isolation, which allows accumulation of random mutations and many different nucleotide substitutions between them that can be detected by molecular markers and give unique DNA barcodes. The use of BIN approach, described here, can aid greatly in making this important question clearer especially under wider examination of other organisms.

Double layer, diluent and anode effects upon the electrodeposition of aluminium from chloroaluminate based ionic liquids.

PubMed

Abbott, Andrew P; Qiu, Fulian; Abood, Hadi M A; Ali, M Rostom; Ryder, Karl S

2010-02-28

The deposition of aluminium from a chloroaluminate based ionic liquid was studied to elucidate the effect of a diluent (toluene) and electrolyte (LiCl) on the deposit morphology. A wide variety of analytical techniques was applied to this system to determine the speciation and mechanism of material growth. These included: (27)Al NMR, FAB-MS, cyclic voltammetry, chronocoulometry, chronopotentiometry, scanning electron microscopy and atomic force microscopy. It was found that under-potential deposition (upd) causes a change in the way in which metal grows on the electrode surface. Metal grows in two regimes which are believed to be nano-material and bulk material. The addition of toluene causes a change in speciation and a decrease in upd which in turn changes the morphology of the deposit obtained and can lead to mirror finish aluminium. The addition of LiCl has the opposite effect encouraging upd and leading to larger crystallites and a dark grey deposit. It is also shown for the first time that under many conditions the rate of the anodic dissolution process is overall rate controlling and one effect of the addition of toluene is to increase the rate of anodic dissolution.

Characterisation of zinc in slags originated from a contaminated sediment by coupling /μ-PIXE, /μ-RBS, /μ-EXAFS and powder EXAFS spectroscopy

NASA Astrophysics Data System (ADS)

Isaure, M. P.; Laboudigue, A.; Manceau, A.; Sarret, G.; Tiffreau, C.; Trocellier, P.

2001-07-01

Depositing dredged sediments on soils is usual but it is a hazardous practice for the local environment when these sediments are polluted by heavy metals. This chemical hazard can be assessed by determining the speciation of metals. In this study, slags highly polluted with Zn and originated from a contaminated dredged sediment were investigated. Zn speciation was studied by laterally resolved techniques such as μ-particle induced X-ray emission (μ-PIXE), μ-Rutherford backscattering spectrometry (μ-RBS), μ-extended X-ray absorption fine structure (μ-EXAFS), and bulk analyses such as powder EXAFS spectroscopy. μ-PIXE and μ-RBS results showed that high concentrations of Zn were associated with S in localised areas at the surface of the slags while moderate amounts of Zn were mainly associated with Fe in the matrix. EXAFS results allowed to identify ZnS and Zn sorbed on ferrihydrite (5Fe 2O 3·9H 2O), proxy for iron oxy-hydroxides, as the main Zn-bearing phases. The occurrence of this Zn-iron oxy-hydroxide is interpreted as a mobilisation of Zn released from ZnS oxidation.

Ionic liquids improved reversed-phase HPLC on-line coupled with ICP-MS for selenium speciation.

PubMed

Chen, Beibei; He, Man; Mao, Xiangju; Cui, Ran; Pang, Daiwen; Hu, Bin

2011-01-15

Room-temperature ionic liquids (RTILs) improved reversed-phase high performance liquid chromatography (RP-HPLC) on-line combined with inductively coupled plasma mass spectrometry (ICP-MS) was developed for selenium speciation. The different parameters affecting the retention behaviors of six target selenium species especially the effect of RTILs as mobile phase additives have been studied, it was found that the mobile phase consisting of 0.4% (v/v) 1-butyl-3-methylimidazolium chloride ([BMIM]Cl), 0.4% (v/v) 1-butyl-2,3-dimethylimidazolium tetrafluroborate ([BMMIM]BF(4)) and 99.2% (v/v) water has effectively improved the peak profile and six target selenium species including Na(2)SeO(3) (Se(IV)), Na(2)SeO(4) (Se(VI)), L-selenocystine (SeCys(2)), D,L-selenomethionine (SeMet), Se-methylseleno-l-cysteine (MeSeCys), seleno-D,L-ethionine (SeEt) were separated in 8 min. In order to validate the accuracy of the method, a Certified Reference Material of SELM-1 yeast sample was analyzed and the results obtained were in good agreement with the certified values. The developed method was also successfully applied to the speciation of selenium in Se-enriched yeasts and clover. For fresh Se-enriched yeast cells, it was found that the spiked SeCys(2) in living yeast cells could be transformed into SeMet. Compared with other ion-pair RP-HPLC-ICP-MS approaches for selenium speciation, the proposed method possessed the advantages including ability to regulate the retention time of the target selenium species by selecting the suitable RTILs and their concentration, simplicity, rapidness and low injection volume, thus providing wide potential applications for elemental speciation in biological systems. Copyright © 2010 Elsevier B.V. All rights reserved.

Flow Injection Photochemical Vapor Generation Coupled with Miniaturized Solution-Cathode Glow Discharge Atomic Emission Spectrometry for Determination and Speciation Analysis of Mercury.

PubMed

Mo, Jiamei; Li, Qing; Guo, Xiaohong; Zhang, Guoxia; Wang, Zheng

2017-10-03

A novel, compact, and green method was developed for the determination and speciation analysis of mercury, based on flow injection photochemical vapor generation (PVG) coupled with miniaturized solution cathode glow discharge-atomic emission spectroscopy (SCGD-AES). The SCGD was generated between a miniature hollow titanium tube and a solution emerging from a glass capillary. Cold mercury vapor (Hg(0)) was generated by PVG and subsequently delivered to the SCGD for excitation, and finally the emission signals were recorded by a miniaturized spectrograph. The detection limits (DLs) of Hg(II) and methylmercury (MeHg) were both determined to be 0.2 μg L -1 . Moreover, mercury speciation analysis could also be performed by using different wavelengths and powers from the UV lamp and irradiation times. Both Hg(II) and MeHg can be converted to Hg(0) for the determination of total mercury (T-Hg) with 8 W/254 nm UV lamp and 60 s irradiation time; while only Hg(II) can be reduced to Hg(0) and determined selectively with 4 W/365 nm UV lamp and 20 s irradiation time. Then, the concentration of MeHg can be calculated by subtracting the Hg(II) from the T-Hg. Because of its similar sensitivity and DL at 8 W/254 nm, the simpler and less toxic Hg(II) was used successfully as a primary standard for the quantification of T-Hg. The novel PVG-SCGD-AES system provides not only a 365-fold improvement in the DL for Hg(II) but also a nonchromatographic method for the speciation analysis of mercury. After validating its accuracy, this method was successfully used for mercury speciation analysis of water and biological samples.

Voltammetric determination of arsenic in high iron and manganese groundwaters.

PubMed

Gibbon-Walsh, Kristoff; Salaün, Pascal; Uroic, M Kalle; Feldmann, Joerg; McArthur, John M; van den Berg, Constant M G

2011-09-15

Determination of the speciation of arsenic in groundwaters, using cathodic stripping voltammetry (CSV), is severely hampered by high levels of iron and manganese. Experiments showed that the interference is eliminated by addition of EDTA, making it possible to determine the arsenic speciation on-site by CSV. This work presents the CSV method to determine As(III) in high-iron or -manganese groundwaters in the field with only minor sample treatment. The method was field-tested in West-Bengal (India) on a series of groundwater samples. Total arsenic was subsequently determined after acidification to pH 1 by anodic stripping voltammetry (ASV). Comparative measurements by ICP-MS as reference method for total As, and by HPLC for its speciation, were used to corroborate the field data in stored samples. Most of the arsenic (78±0.02%) was found to occur as inorganic As(III) in the freshly collected waters, in accordance with previous studies. The data shows that the modified on-site CSV method for As(III) is a good measure of water contamination with As. The EDTA was also found to be effective in stabilising the arsenic speciation for longterm sample storage at room temperature. Without sample preservation, in water exposed to air and sunlight, the As(III) was found to become oxidised to As(V), and Fe(II) oxidised to Fe(III), removing the As(V) by adsorption on precipitating Fe(III)-hydroxides within a few hours. Copyright © 2011 Elsevier B.V. All rights reserved.

Particles, sweat, and tears: a comparative study on bioaccessibility of ferrochromium alloy and stainless steel particles, the pure metals and their metal oxides, in simulated skin and eye contact.

PubMed

Hedberg, Yolanda; Midander, Klara; Wallinder, Inger Odnevall

2010-07-01

Ferrochromium alloys are manufactured in large quantities and placed on the global market for use as master alloys (secondary raw materials), primarily for stainless steel production. Any potential human exposure to ferrochromium alloy particles is related to occupational activities during production and use, with 2 main exposure routes, dermal contact and inhalation and subsequent digestion. Alloy and reference particles exposed in vitro in synthetic biological fluids relevant for these main exposure routes have been investigated in a large research effort combining bioaccessibility; chemical speciation; and material, surface, and particle characteristics. In this paper, data for the dermal exposure route, including skin and eye contact, will be presented and discussed. Bioaccessibility data have been generated for particles of a ferrochromium alloy, stainless steel grade AISI 316L, pure Fe, pure Cr, iron(II,III)oxide, and chromium(III)oxide, upon immersion in artificial sweat (pH 6.5) and artificial tear (pH 8.0) fluids for various time periods. Measured released amounts of Fe, Cr, and Ni are presented in terms of average Fe and Cr release rates and amounts released per amount of particles loaded. The results are discussed in relation to bulk and surface composition of the particles. Additional information, essential to assess the bioavailability of Cr released, was generated by determining its chemical speciation and by providing information on its complexation and oxidation states in both media investigated. The effect of differences in experimental temperature, 30 degrees C and 37 degrees C, on the extent of metal release in artificial sweat is demonstrated. Iron was the preferentially released element in all test media and for all time periods and iron-containing particles investigated. The extent of metal release was highly pH dependent and was also dependent on the medium composition. Released amounts of Cr and Fe were very low (close to the limit of detection, <0.008% of particles released or dissolved as iron or chromium) for the alloy particles (ferrochromium alloy and stainless steel), the pure Cr particles, and the metal oxide particles. The released fraction of Cr (Cr/[Cr + Fe]) varied with the material investigated, the test medium, and the exposure time and cannot be predicted from either the bulk or the surface composition. Chromium was released as noncomplexed Cr(III) and in addition in very low concentrations (<3 microg/L). Nickel released was under the limit of detection (0.5 microg/L), except for ultrafine stainless steel particles (<10 microg/L). It is evident that media chemistry and material properties from a bulk and surface perspective, as well as other particle characteristics, and the chemical speciation of released metals have to be considered when assessing any potential hazard or risk induced by sparingly soluble metal or alloy particles. (c) 2010 SETAC.

Method and apparatus for monitoring mercury emissions

DOEpatents

Durham, Michael D.; Schlager, Richard J.; Sappey, Andrew D.; Sagan, Francis J.; Marmaro, Roger W.; Wilson, Kevin G.

1997-01-01

A mercury monitoring device that continuously monitors the total mercury concentration in a gas. The device uses the same chamber for converting speciated mercury into elemental mercury and for measurement of the mercury in the chamber by radiation absorption techniques. The interior of the chamber is resistant to the absorption of speciated and elemental mercury at the operating temperature of the chamber.

Method and apparatus for monitoring mercury emissions

DOEpatents

Durham, M.D.; Schlager, R.J.; Sappey, A.D.; Sagan, F.J.; Marmaro, R.W.; Wilson, K.G.

1997-10-21

A mercury monitoring device that continuously monitors the total mercury concentration in a gas. The device uses the same chamber for converting speciated mercury into elemental mercury and for measurement of the mercury in the chamber by radiation absorption techniques. The interior of the chamber is resistant to the absorption of speciated and elemental mercury at the operating temperature of the chamber. 15 figs.

EFFECTS OF PH AND COMPETING ANIONS ON THE SPECIATION OF ARSENIC IN FIXED IONIC STRENGTH SOLUTIONS BY SOLID PHASE EXTRACTION CARTRIDGES

EPA Science Inventory

Anion-exchange resins (AERs) separate As(V) and As(lIl) in solution by retaining As(V) and allowing As(lIl) to pass through. AERs offer several advantages including portability, ease of use, and affordability (relative to other As speciation methods). The use of AERs for the inst...

A graph-theoretic approach for inparalog detection.

PubMed

Tremblay-Savard, Olivier; Swenson, Krister M

2012-01-01

Understanding the history of a gene family that evolves through duplication, speciation, and loss is a fundamental problem in comparative genomics. Features such as function, position, and structural similarity between genes are intimately connected to this history; relationships between genes such as orthology (genes related through a speciation event) or paralogy (genes related through a duplication event) are usually correlated with these features. For example, recent work has shown that in human and mouse there is a strong connection between function and inparalogs, the paralogs that were created since the speciation event separating the human and mouse lineages. Methods exist for detecting inparalogs that either use information from only two species, or consider a set of species but rely on clustering methods. In this paper we present a graph-theoretic approach for finding lower bounds on the number of inparalogs for a given set of species; we pose an edge covering problem on the similarity graph and give an efficient 2/3-approximation as well as a faster heuristic. Since the physical position of inparalogs corresponding to recent speciations is not likely to have changed since the duplication, we also use our predictions to estimate the types of duplications that have occurred in some vertebrates and drosophila.

Speciation of sulfur in humic and fulvic acids using X-ray absorption near-edge structure (XANES) spectroscopy

NASA Astrophysics Data System (ADS)

Morra, Matthew J.; Fendorf, Scott E.; Brown, Paul D.

1997-02-01

Sulfur species in soils and sediments have previously been determined indirectly using destructive techniques. A direct and more accurate method for S speciation would improve our understanding of S biogeochemistry. X-ray absorption near edge structure (XANES) spectroscopy was performed on purified humic and fulvic acids from terrestrial and aquatic environments. This methodology allows direct determination of S species using the relationship that exists with the energy required for core electron transitions and in some cases, correlation with additional spectral features. Soil, peat, and aquatic humic acids were dominated by sulfonates with an oxidation state of +5, but also contained ester-bonded sulfates with an oxidation state of +6. Leonardite humic acid contained ester-bonded sulfate and an unidentified S compound with an oxidation state of +4.0. In contrast, high-valent S in soil, peat, and aquatic fulvic acids was exclusively in the form of sulfonic acids. Reduced S species were also present in both humic and fulvic acids. XANES is a valuable method for the speciation of S in humic materials and of potential use in S speciation of unfractionated soils.

Speciation of sulfur in biochar produced from pyrolysis and gasification of oak and corn stover.

PubMed

Cheah, Singfoong; Malone, Shealyn C; Feik, Calvin J

2014-01-01

The effects of feedstock type and biomass conversion conditions on the speciation of sulfur in biochars are not well-known. In this study, the sulfur content and speciation in biochars generated from pyrolysis and gasification of oak and corn stover were determined. We found the primary determinant of the total sulfur content of biomass to be the feedstock from which the biochar is generated, with oak and corn stover biochars containing 160 and 600-800 ppm sulfur, respectively. In contrast, for sulfur speciation, we found the primary determinant to be the temperature combined with the thermochemical conversion method. The speciation of sulfur in biochars was determined using X-ray absorption near-edge structure (XANES), ASTM method D2492, and scanning electron microscopy-energy-dispersive spectroscopy (SEM-EDS). Biochars produced under pyrolysis conditions at 500-600 °C contain sulfate, organosulfur, and sulfide. In some cases, the sulfate contents are up to 77-100%. Biochars produced in gasification conditions at 850 °C contain 73-100% organosulfur. The increase of the organosulfur content as the temperature of biochar production increases suggests a similar sulfur transformation mechanism as that in coal, where inorganic sulfur reacts with hydrocarbon and/or H2 to form organosulfur when the coal is heated. EDS mapping of a biochar produced from corn stover pyrolysis shows individual sulfur-containing mineral particles in addition to the sulfur that is distributed throughout the organic matrix.

Speciation of Sulfur in Biochar Produced from Pyrolysis and Gasification of Oak and Corn Stover

PubMed Central

2015-01-01

The effects of feedstock type and biomass conversion conditions on the speciation of sulfur in biochars are not well-known. In this study, the sulfur content and speciation in biochars generated from pyrolysis and gasification of oak and corn stover were determined. We found the primary determinant of the total sulfur content of biomass to be the feedstock from which the biochar is generated, with oak and corn stover biochars containing 160 and 600–800 ppm sulfur, respectively. In contrast, for sulfur speciation, we found the primary determinant to be the temperature combined with the thermochemical conversion method. The speciation of sulfur in biochars was determined using X-ray absorption near-edge structure (XANES), ASTM method D2492, and scanning electron microscopy–energy-dispersive spectroscopy (SEM–EDS). Biochars produced under pyrolysis conditions at 500–600 °C contain sulfate, organosulfur, and sulfide. In some cases, the sulfate contents are up to 77–100%. Biochars produced in gasification conditions at 850 °C contain 73–100% organosulfur. The increase of the organosulfur content as the temperature of biochar production increases suggests a similar sulfur transformation mechanism as that in coal, where inorganic sulfur reacts with hydrocarbon and/or H2 to form organosulfur when the coal is heated. EDS mapping of a biochar produced from corn stover pyrolysis shows individual sulfur-containing mineral particles in addition to the sulfur that is distributed throughout the organic matrix. PMID:25003702

Partitioning of Dissolved Metals (Fe, Mn, Cu, Cd, Zn, Ni, and Pb) into Soluble and Colloidal Fractions in Continental Shelf and Offshore Waters, Northern California

NASA Astrophysics Data System (ADS)

Fitzsimmons, J. N.; Parker, C.; Sherrell, R. M.

2016-02-01

The physicochemical speciation of trace metals in seawater influences their cycling as essential micronutrients for microorganisms or as tracers of anthropogenic influences on the marine environment. While chemical speciation affects lability, the size of metal complexes influences their ability to be accessed biologically and also influences their fate in the aggregation pathway to marine particles. In this study, we show that multiple trace metals in shelf and open ocean waters off northern California (IRN-BRU cruise, July 2014) have colloidal-sized components. Colloidal fractions were operationally defined using two ultrafiltration methods: a 0.02 µm Anopore membrane and a 10 kDa ( 0.003 µm) cross flow filtration (CFF) system. Together these two methods distinguished small (0.003 - 0.02 µm) and large (0.02 µm - 0.2 µm) colloids. As has been found previously for seawater in other ocean regimes, dissolved Fe had a broad size distribution with 50% soluble (<10 kDa) complexes and both small and large colloidal species. Dissolved Mn had no measurable colloidal component, consistent with its predicted chemical speciation as free Mn(II). Dissolved Cu, which like Fe is thought to be nearly fully organically bound in seawater, was only 25% colloidal, and these colloids were all small. Surprisingly Cd, Ni, and Pb also showed colloidal components (8-20%, 25-40%, and 10-50%) despite their hypothesized low organic speciation. Zn and Pb were nearly completely sorbed onto the Anopore membrane, making CFF the only viable ultrafiltration method for those elements. Zn suffered incomplete recovery ( 50-75%) through the CFF system but showed 30-85% colloidal contribution; thus, verifying a Zn colloidal phase with these methods is challenging. Conclusions will reveal links between the physical and chemical speciation for these metals and what role these metal colloids might have on trace metal exchange between the ocean margin and offshore waters.

Comparative density functional study of the complexes [UO2(CO3)3]4- and [(UO2)3(CO3)6]6- in aqueous solution.

PubMed

Schlosser, Florian; Moskaleva, Lyudmila V; Kremleva, Alena; Krüger, Sven; Rösch, Notker

2010-06-28

With a relativistic all-electron density functional method, we studied two anionic uranium(VI) carbonate complexes that are important for uranium speciation and transport in aqueous medium, the mononuclear tris(carbonato) complex [UO(2)(CO(3))(3)](4-) and the trinuclear hexa(carbonato) complex [(UO(2))(3)(CO(3))(6)](6-). Focusing on the structures in solution, we applied for the first time a full solvation treatment to these complexes. We approximated short-range effects by explicit aqua ligands and described long-range electrostatic interactions via a polarizable continuum model. Structures and vibrational frequencies of "gas-phase" models with explicit aqua ligands agree best with experiment. This is accidental because the continuum model of the solvent to some extent overestimates the electrostatic interactions of these highly anionic systems with the bulk solvent. The calculated free energy change when three mono-nuclear complexes associate to the trinuclear complex, agrees well with experiment and supports the formation of the latter species upon acidification of a uranyl carbonate solution.

Mercury Speciation by X-ray Absorption Fine Structure Spectroscopy and Sequential Chemical Extractions: A Comparison of Speciation Methods

USGS Publications Warehouse

Kim, C.S.; Bloom, N.S.; Rytuba, J.J.; Brown, Gordon E.

2003-01-01

Determining the chemical speciation of mercury in contaminated mining and industrial environments is essential for predicting its solubility, transport behavior, and potential bioavailability as well as for designing effective remediation strategies. In this study, two techniques for determining Hg speciation-X-ray absorption fine structure (XAFS) spectroscopy and sequential chemical extractions (SCE)-are independently applied to a set of samples with Hg concentrations ranging from 132 to 7539 mg/kg to determine if the two techniques provide comparable Hg speciation results. Generally, the proportions of insoluble HgS (cinnabar, metacinnabar) and HgSe identified by XAFS correlate well with the proportion of Hg removed in the aqua regia extraction demonstrated to remove HgS and HgSe. Statistically significant (> 10%) differences are observed however in samples containing more soluble Hg-containing phases (HgCl2, HgO, Hg3S2O 4). Such differences may be related to matrix, particle size, or crystallinity effects, which could affect the apparent solubility of Hg phases present. In more highly concentrated samples, microscopy techniques can help characterize the Hg-bearing species in complex multiphase natural samples.

Geochemical Weathering Increases Lead Bioaccessibility in Semi-Arid Mine Tailings

PubMed Central

Hayes, Sarah M.; Webb, Sam M.; Bargar, John R.; O'Day, Peggy A.; Maier, Raina M.; Chorover, Jon

2012-01-01

Mine tailings can host elevated concentrations of toxic metal(loid)s that represent a significant hazard to surrounding communities and ecosystems. Eolian transport, capable of translocating small (micrometer-sized) particles, can be the dominant mechanism of toxic metal dispersion in arid or semi-arid landscapes. Human exposure to metals can then occur via direct inhalation or ingestion of particulates. The fact that measured doses of total lead (Pb) in geomedia correlate poorly with blood Pb levels highlights a need to better resolve the precise distribution of molecularly-speciated metal-bearing phases in the complex particle mixtures. Species distribution controls bioaccessibility, thereby directly impacting health risk. This study seeks to correlate Pb-containing particle size and mineral composition with lability and bioaccessibility in mine tailings subjected to weathering in a semi-arid environment. We employed X-ray absorption spectroscopy (XAS) and X-ray fluorescence (XRF), coupled with sequential chemical extractions, to study Pb speciation in tailings from the semi-arid Arizona Klondyke State Superfund Site. Representative samples ranging in pH from 2.6 to 5.4 were selected for in-depth study of Pb solid-phase speciation. The principle lead-bearing phase was plumbojarosite (PbFe6(SO4)4(OH)12), but anglesite (PbSO4) and iron oxide-sorbed Pb were also observed. Anglesite, the most bioavailable mineral species of lead identified in this study, was enriched in surficial tailings samples, where Pb concentrations in the clay size fraction were 2–3 times higher by mass relative to bulk. A mobile and bioaccessible Pb phase accumulates in surficial tailings, with a corresponding increase in risk of human exposure to atmospheric particles. PMID:22553941

Speciation of phosphorus in the continental shelf sediments in the Eastern Arabian Sea

NASA Astrophysics Data System (ADS)

Acharya, Shiba Shankar; Panigrahi, Mruganka Kumar; Kurian, John; Gupta, Anil Kumar; Tripathy, Subhasish

2016-03-01

The distributions of various forms of phosphorus (P) and their relation with sediment geochemistry in two core sediments near Karwar and Mangalore offshore have been studied through the modified SEDEX procedure (Ruttenberg et al., 2009) and bulk chemical analysis. The present study provides the first quantitative analysis of complete phosphorus speciation in the core sediments of the Eastern Arabian shelf. The chemical index of alteration (CIA), chemical Index of Weathering (CIW) and Al-Ti-Zr ternary diagram suggest low to moderate source area weathering of granodioritic to tonalitic source rock composition, despite the intense orographic rainfall in the source area. Due to the presence of same source rock and identical oxic depositional environment, the studied sediments show the same range of variation of total phosphorus (24 to 83 μmol/g) with a down-depth depleting trend. Organic bound P and detrital P are the two major chemical forms followed by iron-bound P, exchangeable/loosely bound P and authigenic P. The authigenic P content in the sediments near Mangalore coast varies linearly with calcium (r=0.88) unlike that of Karwar coast. The different reactive-phosphorus pools exhibit identical depleting trend with depth. This indicates that the phosphorus released from the organic matter and Fe bound fractions are prevented from precipitating as authigenic phosphates in the deeper parts of the sediment column. The low concentration of total P, dominance of detrital non-reactive fraction of P and inhibition of formation of authigenic phosphate result in the absence of active phosphatization in the Eastern Arabian Shelf in the studied region. High sedimentation rate (35-58 cm/kyr) and absence of winnowing effect appear to be the dominant factor controlling the P-speciation in the studied sediments.

Field and laboratory arsenic speciation methods and their application to natural-water analysis

USGS Publications Warehouse

Bednar, A.J.; Garbarino, J.R.; Burkhardt, M.R.; Ranville, J.F.; Wildeman, T.R.

2004-01-01

The toxic and carcinogenic properties of inorganic and organic arsenic species make their determination in natural water vitally important. Determination of individual inorganic and organic arsenic species is critical because the toxicology, mobility, and adsorptivity vary substantially. Several methods for the speciation of arsenic in groundwater, surface-water, and acid mine drainage sample matrices using field and laboratory techniques are presented. The methods provide quantitative determination of arsenite [As(III)], arsenate [As(V)], monomethylarsonate (MMA), dimethylarsinate (DMA), and roxarsone in 2-8min at detection limits of less than 1??g arsenic per liter (??g AsL-1). All the methods use anion exchange chromatography to separate the arsenic species and inductively coupled plasma-mass spectrometry as an arsenic-specific detector. Different methods were needed because some sample matrices did not have all arsenic species present or were incompatible with particular high-performance liquid chromatography (HPLC) mobile phases. The bias and variability of the methods were evaluated using total arsenic, As(III), As(V), DMA, and MMA results from more than 100 surface-water, groundwater, and acid mine drainage samples, and reference materials. Concentrations in test samples were as much as 13,000??g AsL-1 for As(III) and 3700??g AsL-1 for As(V). Methylated arsenic species were less than 100??g AsL-1 and were found only in certain surface-water samples, and roxarsone was not detected in any of the water samples tested. The distribution of inorganic arsenic species in the test samples ranged from 0% to 90% As(III). Laboratory-speciation method variability for As(III), As(V), MMA, and DMA in reagent water at 0.5??g AsL-1 was 8-13% (n=7). Field-speciation method variability for As(III) and As(V) at 1??g AsL-1 in reagent water was 3-4% (n=3). ?? 2003 Elsevier Ltd. All rights reserved.

Speciation of animal fat: Needs and challenges.

PubMed

Hsieh, Yun-Hwa Peggy; Ofori, Jack Appiah

2017-05-24

The use of pork fat is a concern for Muslims and Jews, who for religious reasons avoid consuming anything that is pig-derived. The use of bovine materials, including beef fat, is prohibited in Hinduism and may also pose a risk of carrying the infectious agent for bovine spongiform encephalopathy. Vegetable oils are sometimes adulterated with animal fat or pork fat with beef fat for economic gain. The development of methods to determine the species origin of fat has therefore become a priority due to the complex and global nature of the food trade, which creates opportunities for the fraudulent use of these animal fats as food ingredients. However, determining the species origin of fats in processed foods or composite blends is an arduous task as the adulterant has a composition that is very similar to that of the original fat or oil. This review examines some of the methods that have been developed for fat speciation, including both fat-based and DNA-based methods, their shortcomings, and the need for additional alternatives. Protein-based methods, specifically immunoassays targeting residual proteins in adipose tissue, that are being explored by researchers as a new tool for fat speciation will also be discussed.

Iodine speciation in coastal and inland bathing waters and seaweeds extracts using a sequential injection standard addition flow-batch method.

PubMed

Santos, Inês C; Mesquita, Raquel B R; Bordalo, Adriano A; Rangel, António O S S

2015-02-01

The present work describes the development of a sequential injection standard addition method for iodine speciation in bathing waters and seaweeds extracts without prior sample treatment. Iodine speciation was obtained by assessing the iodide and iodate content, the two inorganic forms of iodine in waters. For the determination of iodide, an iodide ion selective electrode (ISE) was used. The indirect determination of iodate was based on the spectrophotometric determination of nitrite (Griess reaction). For the iodate measurement, a mixing chamber was employed (flow batch approach) to explore the inherent efficient mixing, essential for the indirect determination of iodate. The application of the standard addition method enabled detection limits of 0.14 µM for iodide and 0.02 µM for iodate, together with the direct introduction of the target water samples, coastal and inland bathing waters. The results obtained were in agreement with those obtained by ICP-MS and a colorimetric reference procedure. Recovery tests also confirmed the accuracy of the developed method which was effectively applied to bathing waters and seaweed extracts. Copyright © 2014 Elsevier B.V. All rights reserved.

Aqueous and solid phase speciation of arsenic in a Bengali aquifer using IC-ICP-MS and EXAFS

NASA Astrophysics Data System (ADS)

Gault, A. G.; Davidson, L. E.; Lythgoe, P. R.; Charnock, J. M.; Chatterjee, D.; Abou-Shakra, F. R.; Walker, H. J.; Polya, D. A.

2003-04-01

Contamination of groundwater and drinking water supplies with arsenic has been reported in many parts of the world and constitutes a serious public health threat. Nowhere is this more apparent than in West Bengal and Bangladesh where arsenic concentrations exceed both World Health Organisation (WHO) and national limits in drinking water supplies leading to what has been described as the worst mass poisoning of a human population in history. Knowledge of both aqueous and solid phase speciation of arsenic in such hazardous arsenic-rich groundwaters is crucial to understanding the processes controlling arsenic release. We report here preliminary work involving the determination of dissolved arsenic speciation in West Bengali groundwaters and extended X-ray absorption fine structure (EXAFS) analysis of the associated sediment. Groundwater samples collected from Nadia district, West Bengal were analysed for arsenic speciation by ion chromatography-inductively coupled plasma-mass spectrometry (IC-ICP-MS) within 14 days of collection. Total arsenic concentrations exceeding 850 ug/L were determined; inorganic arsenic constituted the bulk of the dissolved arsenic burden with As(III) as the dominant form. Minor amounts of methylated arsenicals were also detected, however, their concentration did not exceed 5 ug/L. The local coordination environment of arsenic in sediment associated with such groundwaters was probed using K-edge As EXAFS. This revealed that arsenic exists predominantly in its oxidised form, As(V), most likely adsorbed as bidentate arsenate tetrahedra on metal (Fe and/or Al) oxide/hydroxide surfaces, although incorporation of arsenic into a metal oxide structure cannot be unequivocally ruled out. Arsenic was found to occur in several different coordination environments and this, together with the low concentration (< 5 ug/g) of arsenic in the sediment, prevented the unambiguous assignment of the second coordination sphere. The analysis of the trends of key groundwater constituents in our data suggest that arsenic is released due to the reductive dissolution of arsenic laden-hydrous ferric oxides, however, further work is required to fully evaluate the mode of arsenic release.

SPECIATE 4.3: Addendum to SPECIATE 4.2--Speciation database development documentation

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency's (EPA) repository of volatile organic gas and particulate matter (PM) speciation profiles of air pollution sources. Among the many uses of speciation data, these source profiles are used to: (1) create speciated emissions inve...

SPECIATE 4.0: SPECIATION DATABASE DEVELOPMENT DOCUMENTATION--FINAL REPORT

EPA Science Inventory

SPECIATE is the U.S. EPA's repository of total organic compounds (TOC) and particulate matter (PM) speciation profiles of air pollution sources. This report documents how EPA developed the SPECIATE 4.0 database that replaces the prior version, SPECIATE 3.2. SPECIATE 4.0 includes ...

Chemical speciation and bioavailability of rare earth elements (REEs) in the ecosystem: a review.

PubMed

Khan, Aysha Masood; Bakar, Nor Kartini Abu; Bakar, Ahmad Farid Abu; Ashraf, Muhammad Aqeel

2017-10-01

Rare earths (RE), chemically uniform group of elements due to similar physicochemical behavior, are termed as lanthanides. Natural occurrence depends on the geological circumstances and has been of long interest for geologist as tools for further scientific research into the region of ores, rocks, and oceanic water. The review paper mainly focuses to provide scientific literature about rare earth elements (REEs) with potential environmental and health effects in understanding the research. This is the initial review of RE speciation and bioavailability with current initiative toward development needs and research perceptive. In this paper, we have also discussed mineralogy, extraction, geochemistry, analytical methods of rare earth elements. In this study, REEs with their transformation and vertical distribution in different environments such as fresh and seawater, sediments, soil, weathering, transport, and solubility have been reported with most recent literature along key methods of findings. Speciation and bioavailability have been discussed in detail with special emphasis on soil, plant, and aquatic ecosystems and their impacts on the environment. This review shows that REE gained more importance in last few years due to their detrimental effects on living organisms, so their speciation, bioavailability, and composition are much more important to evaluate their health risks and are discussed thoroughly as well.

Carbon speciation in ash, residual waste and contaminated soil by thermal and chemical analyses.

PubMed

Kumpiene, Jurate; Robinson, Ryan; Brännvall, Evelina; Nordmark, Désirée; Bjurström, Henrik; Andreas, Lale; Lagerkvist, Anders; Ecke, Holger

2011-01-01

Carbon in waste can occur as inorganic (IC), organic (OC) and elemental carbon (EC) each having distinct chemical properties and possible environmental effects. In this study, carbon speciation was performed using thermogravimetric analysis (TGA), chemical degradation tests and the standard total organic carbon (TOC) measurement procedures in three types of waste materials (bottom ash, residual waste and contaminated soil). Over 50% of the total carbon (TC) in all studied materials (72% in ash and residual waste, and 59% in soil) was biologically non-reactive or EC as determined by thermogravimetric analyses. The speciation of TOC by chemical degradation also showed a presence of a non-degradable C fraction in all materials (60% of TOC in ash, 30% in residual waste and 13% in soil), though in smaller amounts than those determined by TGA. In principle, chemical degradation method can give an indication of the presence of potentially inert C in various waste materials, while TGA is a more precise technique for C speciation, given that waste-specific method adjustments are made. The standard TOC measurement yields exaggerated estimates of organic carbon and may therefore overestimate the potential environmental impacts (e.g. landfill gas generation) of waste materials in a landfill environment. Copyright © 2010 Elsevier Ltd. All rights reserved.

Adding to the Mercury Speciation Toolbox

NASA Astrophysics Data System (ADS)

Fitts, J. P.; Northrup, P. A.; Chidambaram, D.; Kalb, P. D.

2007-12-01

Mercury was used to separate lithium-6 isotope for weapons production at the Y-12 Plant in Oak Ridge, TN in the 1950s and 1960s. A large portion of the waste Hg entered the environment and continues to move throughout the sub-surface and surface waters in the area. Environmental management of Hg contamination within this complex hydrologic system, where Hg speciation and the mobile fraction have been found to vary widely, will require ongoing characterization and predictive modeling of Hg speciation. State-of-the-art spectroscopic tools that can directly probe Hg speciation in preserved aqueous and sediment samples with greater sensitivity, however, are required to determine rates and mechanisms of biogeochemical reactions. We will present the first results demonstrating the use of x-ray absorption spectroscopy (XAS) at the Hg M5 edge (2295 eV) to fingerprint Hg species. Heavy-metal M5 absorption edges can have very sharp features due to local electron transitions, and therefore, we are developing this edge as a tool for quantitative measurement of Hg species. In addition, sulfur speciation using the sulfur K absorption edge, which is at a similar energy (2472 eV), can be measured in the same scan as the Hg M5 edge. Potentially important organic and inorganic sulfur species (sulfide, disulfide, elemental sulfur, sulfite and sulfate) are readily differentiated, and thereby, provides an independent method for monitoring the redox state of the system along with changes in S-Hg bonding. We will also present x-ray microprobe 2-D concentration maps of Hg and other elements at the grain and pore scales to identify its microscopic distribution and chemical associations. When used in combination with established sequential extraction and direct spectroscopic methods, the addition of XAS at the Hg M5 edge should provide a significant advancement in the determination of Hg speciation in complex biogeochemical environments.

Recent Advances in On-Line Methods Based on Extraction for Speciation Analysis of Chromium in Environmental Matrices.

PubMed

Trzonkowska, Laura; Leśniewska, Barbara; Godlewska-Żyłkiewicz, Beata

2016-07-03

The biological activity of Cr(III) and Cr(VI) species, their chemical behavior, and toxic effects are dissimilar. The speciation analysis of Cr(III) and Cr(VI) in environmental matrices is then of great importance and much research has been devoted to this area. This review presents recent developments in on-line speciation analysis of chromium in such samples. Flow systems have proved to be excellent tools for automation of sample pretreatment, separation/preconcentration of chromium species, and their detection by various instrumental techniques. Analytical strategies used in chromium speciation analysis discussed in this review are divided into categories based on selective extraction/separation of chromium species on solid sorbents and liquid-liquid extraction of chromium species. The most popular strategy is that based on solid-phase extraction. Therefore, this review shows the potential of novel materials designed and used for selective binding of chromium species. The progress in miniaturization of measurement systems is also presented.

A simple method using on-line continuous leaching and ion exchange chromatography coupled to inductively coupled plasma mass spectrometry for the speciation analysis of bio-accessible arsenic in rice.

PubMed

Horner, Nolan S; Beauchemin, Diane

2012-03-02

A simple method for the speciation analysis of bio-accessible arsenic (As) in rice was developed using a continuous on-line leaching method to release the bio-accessible fraction. The continuous on-line leaching method has several advantages over commonly used batch methods including quicker and easier sample preparation, reduced risk of contamination and access to real time leaching data. The bio-accessibility of As in the samples was monitored using inductively coupled plasma mass spectrometry (ICP-MS). Results from a certified reference material as well as cooked and uncooked white rice showed that the majority of As was leached by saliva. Results obtained using the continuous on-line leaching method were comparable to those obtained using a batch method. Speciation analysis of the saliva leachate was performed using ion exchange chromatography coupled to ICP-MS. The four most toxic forms of As (As(III), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA) and As(V)) were clearly separated within 5 min in a single chromatographic run. Over 92% of bio-accessible As in the certified reference material and uncooked white rice sample was in the form of DMA and As(V), whereas it was present as DMA and As(III) in the cooked white rice. Copyright © 2011 Elsevier B.V. All rights reserved.

Iron Speciation in the Subtropical Waters East of New Zealand using Multi Detection Window CLE-AdCSV Titrations.

NASA Astrophysics Data System (ADS)

Chandrasekhar, Anoop; Sander, Sylvia; Milnes, Angie; Boyd, Philip

2015-04-01

Iron plays a significant role in the ocean productivity as a micro nutrient that facilitates the growth of marine phytoplankton and microbes. The bioavailability of iron in the ocean depends on it speciation. Iron is bio available in its dissolved form and about 99.9% of dissolved iron in seawater is organically complexed with natural ligands. The competitive ligand equilibration - adsorptive cathodic stripping voltammetry (CLE-AdCSV) is the widely used technique to examine Fe speciation. The method has its own limitations. The analytical window employed in this technique has a distinct impact on Fe speciation results (Buck, Moffett et al. 2012). Recently, (Pizeta, Sander et al. in preparation) have shown that the accuracy of complexometric titrations improve if multiple analytical windows (MAW) are solved as a united dataset. Several programs are now available that enable this approach with the KMS (Kineteql.xls , Hudson 2014), which is based on an Excel application based on speciation calculation (Hudson, Rue et al. 2003, Sander, Hunter et al. 2011), being one of them. In the present work, the unified MAW data analysis method is applied to determine iron speciation by CLE-AdCSV with salicyl aldoxime (SA) (Abualhaija and van den Berg 2014) in real seawater samples from the Spring bloom FeCycle III voyage, which took place in an anticyclonic eddy in subtropical waters east of New Zealand in spring 2012. Two different analytical windows (5 and 15µM SA) were applied to samples from depth profiles taken during this cruise. The data obtained was analysed using the program KMS (Kineteql.xls). Most samples only returned one Fe-binding ligands class. Higher ligand concentrations were observed in the upper water column and the stability constants were above 22 (e.g. 22.25 ± 0.21 for station 63). Our results will be discussed in the context of microbial community distribution as well as other biogeochemical parameters. Abualhaija, M. M. and C. M. G. van den Berg (2014). "Chemical speciation of iron in seawater using catalytic cathodic stripping voltammetry with ligand competition against salicylaldoxime." Marine Chemistry 164(0): 60-74. Buck, K. N., J. Moffett, K. A. Barbeau, R. M. Bundy, Y. Kondo and J. Wu (2012). "The organic complexation of iron and copper: an intercomparison of competitive ligand exchange-adsorptive cathodic stripping voltammetry (CLE-ACSV) techniques " Limnology and Oceanography: Methods 10: 496-515. Hudson, R. J. M., E. L. Rue and K. W. Bruland (2003). "Modeling Complexometric Titrations of Natural Water Samples." Environ. Sci. Tech. 37: 1553-1562. Pizeta, I., S. G. Sander, O. Baars, K. Buck, R. Bundy, G. Carrasco, P. Croot, C. Garnier, L. Gerringa, M. Gledhill, K. Hirose, D. R. Hudson, Y. Kondo-Jacquot, L. Laglera, D. Omanovic, M. Rijkenberg, B. Twining and M. Wells (in preparation). "Intercomparison of estimating metal binding ligand parameters from simulated titration data using different fitting approaches." for Limnology and Oceanography: Methods. Sander, S. G., K. A. Hunter, H. Harms and M. Wells (2011). "Numerical approach to speciation and estimation of parameters used in modeling trace metal bioavailability." Environmental Science and Technology 45(15): 6388-6395.

Chromosomal Speciation in the Genomics Era: Disentangling Phylogenetic Evolution of Rock-wallabies.

PubMed

Potter, Sally; Bragg, Jason G; Blom, Mozes P K; Deakin, Janine E; Kirkpatrick, Mark; Eldridge, Mark D B; Moritz, Craig

2017-01-01

The association of chromosome rearrangements (CRs) with speciation is well established, and there is a long history of theory and evidence relating to "chromosomal speciation." Genomic sequencing has the potential to provide new insights into how reorganization of genome structure promotes divergence, and in model systems has demonstrated reduced gene flow in rearranged segments. However, there are limits to what we can understand from a small number of model systems, which each only tell us about one episode of chromosomal speciation. Progressing from patterns of association between chromosome (and genic) change, to understanding processes of speciation requires both comparative studies across diverse systems and integration of genome-scale sequence comparisons with other lines of evidence. Here, we showcase a promising example of chromosomal speciation in a non-model organism, the endemic Australian marsupial genus Petrogale . We present initial phylogenetic results from exon-capture that resolve a history of divergence associated with extensive and repeated CRs. Yet it remains challenging to disentangle gene tree heterogeneity caused by recent divergence and gene flow in this and other such recent radiations. We outline a way forward for better integration of comparative genomic sequence data with evidence from molecular cytogenetics, and analyses of shifts in the recombination landscape and potential disruption of meiotic segregation and epigenetic programming. In all likelihood, CRs impact multiple cellular processes and these effects need to be considered together, along with effects of genic divergence. Understanding the effects of CRs together with genic divergence will require development of more integrative theory and inference methods. Together, new data and analysis tools will combine to shed light on long standing questions of how chromosome and genic divergence promote speciation.

Speciation of Mg in biogenic calcium carbonates

NASA Astrophysics Data System (ADS)

Farges, F.; Meibom, A.; Flank, A.-M.; Lagarde, P.; Janousch, M.; Stolarski, J.

2009-11-01

A selection of marine biominerals, mostly aragonitic coral skeletons were probed at the Mg K-edge by XANES spectroscopy coupled to μXRF methods and compared to an extensive set of relevant model compounds (silicates, carbonates, oxides and organic). Extensive methodologies are required to better describe the speciation of Mg in those minerals. A combination of ab-initio XANES calculations for defective clusters around Mg in aragonite together with wavelets analyzes of the XANES region are required to robustly interpret the spectra. When using those methodologies, the speciation of Mg ranges from a magnesite-type environment in some scleractinian corals to an organic-type environment. In all environments, the Mg-domains probed appear to be less than 1 nm in size.

Selective Separation and Determination of Heavy Metals (Cd, Pb, Cr) Speciation Forms from Hortic Antrosols

NASA Astrophysics Data System (ADS)

Bulgariu, D.; Bulgariu, L.

2009-04-01

The speciation, inter-phases distribution and biodisponibility of heavy metals in soils represent one of main problem of environmental geochemistry and agro-chemistry. This problem is very important in case of hortic antrosols (soils from glasshouses) for the elimination of agricultural products (fruits, vegetables) contamination with heavy metals. In soils from glass houses, the speciation and inter-phases distribution processes of heavy metals have a particular dynamic, different in comparison with those from non-protected soils. The predominant distribution forms of heavy metals in such soils types are: complexes with low mass organic molecules, organic-mineral complexes, complexes with inorganic ligands (hydroxide-complexes, carbonate-complexes, sulphate-complexes, etc.) and basic salts. All of these have high stabilities in conditions of soils from glass houses, and in consequence, the separation and determination of speciation forms (which is directly connected with biodisponibility of heavy metals) by usual methods id very difficult and has a high uncertain degree. In this study is presented an original method for the selective separation and differentiation of speciation forms of heavy metals from glass houses soils, which is based by the combination of solid-liquid sequential extraction (SPE) with the extraction in aqueous polymer-inorganic salt two-phase systems (ABS). The soil samples used for this study have been sampled from three different locations (glass houses from Iasi, Barlad and Bacau - Romania) where the vegetables cultivation have bee performed by three different technologies. In this way was estimated the applicability and the analytical limits of method proposed by as, in function of the chemical-mineralogical and physical-chemical characteristics of soils. As heavy metals have been studied cadmium, lead and chromium, all being known for their high toxicity. The procedure used for the selective separation and differentiation of speciation forms of heavy metals from glass houses soils has two main steps: (i) non-destructive separation of chemical-mineralogical associations and aggregates from soils samples - for this the separation method with heavy liquids (bromophorme) and isodynamic magnetic method have been used; (ii) sequential extraction of heavy metals from soil fractions separated in the first step, by using combined SPE-ABS procedure. For the preparation of combined extraction systems was used polyethylene glycol (with different molecular mass: 2000, 4000 and 8000). As phase-forming inorganic salts and as selective extracting agents we have used different usual inorganic reagents. The type and concentration of phase-forming salts have been selected in function of, both nature of extracted heavy metals and chemical-mineralogical characteristics of soil samples. The experimental parameters investigated in this study are: molecular mass of polyethylene glycol and the concentration of polymeric solutions, nature and concentration of phase-forming salts, nature and concentration of extracting agents, pH in extraction system phase, type of extracted heavy metals, type of speciation forms of heavy metals and their concentrations. All these factors can influence significantly the efficiency and the selectivity of separation process. The experimental results have indicate that the combined SPE-ABS extraction systems have better separation efficiency, in comparison with traditional SPE systems and ca realized a accurate discrimination between speciation forms of heavy metals from soils. Under these conditions, the estimation of inter-phases distribution and biodisponibility of heavy metals has a high precision. On the other hand, when the combined SPE-ABS systems are used, the concomitant extraction of the elements from the same geochemical association with studied heavy metals (inevitable phenomena in case of separation by SPE procedures) is significant diminished. This increases the separation selectivity and facilitated the more accurate determination of speciation forms concentration. By adequate selection of extraction conditions can be realized the selective separation of organic-mineral complexes, which will permit to perform detailed studies about the structure and chemical composition of these. Acknowledgments The authors would like to acknowledge the financial support from Romanian Ministry of Education and Research (Project PNCDI 2-D5 no. 51045/07).

SPECIATE and using the Speciation Tool to prepare VOC and PM chemical speciation profiles for air quality modeling

EPA Science Inventory

This product provides training to air pollution inventory and modeling professionals to understand the US EPA's SPECIATE database base and Speciation Tool and their use to develop speciated emission inventories.

SPECIATE's VOC and PM Speciation Profiles and Their use to Prepare for Air quality Modeling (2017 EIC)

EPA Pesticide Factsheets

This training provides general concepts on chemical speciation, the SPECIATE database and browser, and how to use the Speciation Tool to create model ready speciation inputs for a photochemical air quality model.

SPECIATE 4.2: speciation Database Development Documentation

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency's (EPA) repository of volatile organic gas and particulate matter (PM) speciation profiles of air pollution sources. Among the many uses of speciation data, these source profiles are used to: (1) create speciated emissions inve...

Sequestration of arsenic in ombrotrophic peatlands

NASA Astrophysics Data System (ADS)

Rothwell, James; Hudson-Edwards, Karen; Taylor, Kevin; Polya, David; Evans, Martin; Allott, Tim

2014-05-01

Peatlands can be important stores of arsenic but we are lacking spectroscopic evidence of the sequestration pathways of this toxic metalloid in peatland environments. This study reports on the solid-phase speciation of anthropogenically-derived arsenic in atmospherically contaminated peat from the Peak District National Park (UK). Surface and sub-surface peat samples were analysed by synchrotron X-ray absorption spectroscopy on B18 beamline at Diamond Light Source (UK). The results suggest that there are contrasting arsenic sequestration mechanisms in the peat. The bulk arsenic speciation results, in combination with strong arsenic-iron correlations at the surface, suggest that iron (hydr)oxides are key phases for the immobilisation of arsenic at the peat surface. In contrast, the deeper peat samples are dominated by arsenic sulphides (arsenopyrite, realgar and orpiment). Given that these peats receive inputs solely from the atmosphere, the presence of these sulphide phases suggests an in-situ authigenic formation. Redox oscillations in the peat due to a fluctuating water table and an abundant store of legacy sulphur from historic acid rain inputs may favour the precipitation of arsenic sequestering sulphides in sub-surface horizons. Oxidation-induced loss of these arsenic sequestering sulphur species by water table drawdown has important implications for the mobility of arsenic and the quality of waters draining peatlands.

Iron solubility related to particle sulfur content in source emission and ambient fine particles.

PubMed

Oakes, M; Ingall, E D; Lai, B; Shafer, M M; Hays, M D; Liu, Z G; Russell, A G; Weber, R J

2012-06-19

The chemical factors influencing iron solubility (soluble iron/total iron) were investigated in source emission (e.g., biomass burning, coal fly ash, mineral dust, and mobile exhaust) and ambient (Atlanta, GA) fine particles (PM2.5). Chemical properties (speciation and mixing state) of iron-containing particles were characterized using X-ray absorption near edge structure (XANES) spectroscopy and micro-X-ray fluorescence measurements. Bulk iron solubility (soluble iron/total iron) of the samples was quantified by leaching experiments. Major differences were observed in iron solubility in source emission samples, ranging from low solubility (<1%, mineral dust and coal fly ash) up to 75% (mobile exhaust and biomass burning emissions). Differences in iron solubility did not correspond to silicon content or Fe(II) content. However, source emission and ambient samples with high iron solubility corresponded to the sulfur content observed in single particles. A similar correspondence between bulk iron solubility and bulk sulfate content in a series of Atlanta PM2.5 fine particle samples (N = 358) further supported this trend. In addition, results of linear combination fitting experiments show the presence of iron sulfates in several high iron solubility source emission and ambient PM2.5 samples. These results suggest that the sulfate content (related to the presence of iron sulfates and/or acid-processing mechanisms by H(2)SO(4)) of iron-containing particles is an important proxy for iron solubility.

Chromium speciation in environmental samples using a solid phase spectrophotometric method

NASA Astrophysics Data System (ADS)

Amin, Alaa S.; Kassem, Mohammed A.

2012-10-01

A solid phase extraction technique is proposed for preconcentration and speciation of chromium in natural waters using spectrophotometric analysis. The procedure is based on sorption of chromium(III) as 4-(2-benzothiazolylazo)2,2'-biphenyldiol complex on dextran-type anion-exchange gel (Sephadex DEAE A-25). After reduction of Cr(VI) by 0.5 ml of 96% concentrated H2SO4 and ethanol, the system was applied to the total chromium. The concentration of Cr(VI) was calculated as the difference between the total Cr and the Cr(III) content. The influences of some analytical parameters such as: pH of the aqueous solution, amounts of 4-(2-benzothiazolylazo)2,2'-biphenyldiol (BTABD), and sample volumes were investigated. The absorbance of the gel, at 628 and 750 nm, packed in a 1.0 mm cell, is measured directly. The molar absorptivities were found to be 2.11 × 107 and 3.90 × 107 L mol-1 cm-1 for 500 and 1000 ml, respectively. Calibration is linear over the range 0.05-1.45 μg L-1 with RSD of <1.85% (n = 8.0). Using 35 mg exchanger, the detection and quantification limits were 13 and 44 ng L-1 for 500 ml sample, whereas for 1000 ml sample were 8.0 and 27 ng L-1, respectively. Increasing the sample volume can enhance the sensitivity. No considerable interferences have been observed from other investigated anions and cations on the chromium speciation. The proposed method was applied to the speciation of chromium in natural waters and total chromium preconcentration in microwave digested tobacco, coffee, tea, and soil samples. The results were simultaneously compared with those obtained using an ET AAS method, whereby the validity of the method has been tested.

Microbial-driven arsenic cycling in rice paddies amended with monosodium methanearsonate

NASA Astrophysics Data System (ADS)

Maguffin, S. C.; McClung, A.; Rohila, J. S.; Derry, L. A.; Huang, R.; Reid, M. C.

2017-12-01

Rice consumption is the second largest contributor to human arsenic exposure worldwide and is linked to many serious diseases. Because rice is uniquely adapted for agricultural production under flooded soils, arsenic species solubilized in such environments can be effectively transported into plant tissue via root transporters. Through this process, both inorganic and organic (methylated) arsenic species can accumulate to problematic concentrations and may affect grain yield as well as crop value. The distribution of these species in plant tissue is determined by arsenic sources, as well as enzymatic redox and methylation-demethylation reactions in soils and pore water. Historic use of organoarsenic-based pesticides in US agriculture may provide an enduring source of arsenic in rice paddies. However, it is unclear how persistent these organic species are in the adsorbed phase or how available they remain to rice cultivars throughout the growing season. We conducted a field experiment in a 2x2 factorial design examining the effects of irrigation methods (continuous flooding and alternate wetting and drying) and monosodium methanearsonate (MSMA) application on the abundance and speciation of arsenic in pore water, soil, and rice plant tissues. We monitored arsenic speciation and partitioning between these reservoirs at semi-weekly to semi-monthly frequencies. Pore water arsenic speciation was determined using LC-ICP-MS, and X-ray absorption near-edge structure (XANES) analysis was employed to speciate the arsenic within solid-phase soil and plant tissue throughout the growing season. These data help clarify the role of two irrigation methods and MSMA amendments for arsenic bioavailability and speciation in rice. Furthermore, the study illuminates the significance of microbial metabolism in the reapportionment of arsenic within the soil-plant-water system and its impact on arsenic levels in rice grains.

Organotin speciation in environmental matrices by automated on-line hydride generation-programmed temperature vaporization-capillary gas chromatography-mass spectrometry detection.

PubMed

Serra, H; Nogueira, J M F

2005-11-11

In the present contribution, a new automated on-line hydride generation methodology was developed for dibutyltin and tributyltin speciation at the trace level, using a programmable temperature-vaporizing inlet followed by capillary gas chromatography coupled to mass spectrometry in the selected ion-monitoring mode acquisition (PTV-GC/MS(SIM)). The methodology involves a sequence defined by two running methods, the first one configured for hydride generation with sodium tetrahydroborate as derivatising agent and the second configured for speciation purposes, using a conventional autosampler and data acquisition controlled by the instrument's software. From the method-development experiments, it had been established that injector configuration has a great effect on the speciation of the actual methodology, particularly, the initial inlet temperature (-20 degrees C; He: 150 ml/min), injection volume (2 microl) and solvent characteristics using the solvent venting mode. Under optimized conditions, a remarkable instrumental performance including very good precision (RSD < 4%), excellent linear dynamic range (up to 50 microg/ml) and limits of detection of 0.12 microg/ml and 9 ng/ml, were obtained for dibutyltin and tributyltin, respectively. The feasibility of the present methodology was validated through assays upon in-house spiked water (2 ng/ml) and a certified reference sediment matrix (Community Bureau of Reference, CRM 462, Nr. 330 dibutyltin: 68+/-12 ng/g; tributyltin: 54+/-15 ng/g on dry mass basis), using liquid-liquid extraction (LLE) and solid-phase extraction (SPE) sample enrichment and multiple injections (2 x 5 microl) for sensitivity enhancement. The methodology evidenced high reproducibility, is easy to work-up, sensitive and showed to be a suitable alternative to replace the currently dedicated analytical systems for organotin speciation in environmental matrices at the trace level.

Characterization and measurement of natural gas trace constituents. Volume 1. Arsenic. Final report, June 1989-October 1993

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chao, S.S.; Attari, A.

1995-01-01

The discovery of arsenic compounds, as alkylarsines, in natural gas prompted this research program to develop reliable measurement techniques needed to assess the efficiency of removal processes for these environmentally sensitive substances. These techniques include sampling, speciation, quantitation and on-line instrumental methods for monitoring the total arsenic concentration. The current program has yielded many products, including calibration standards, arsenic-specific sorbents, sensitive analytical methods and instrumentation. Four laboratory analytical methods have been developed and successfully employed for arsenic determination in natural gas. These methods use GC-AED and GC-MS instruments to speciate alkylarsines, and peroxydisulfate extraction with FIAS, special carbon sorbent withmore » XRF and an IGT developed sorbent with GFAA for total arsenic measurement.« less

Electrochemical vapor generation of selenium species after online photolysis and reduction by UV-irradiation under nano TiO2 photocatalysis and its application to selenium speciation by HPLC coupled with atomic fluorescence spectrometry.

PubMed

Liang, Jing; Wang, Qiuquan; Huang, Benli

2005-01-01

An online UV photolysis and UV/TiO2 photocatalysis reduction device (UV-UV/TiO2 PCRD) and an electrochemical vapor generation (ECVG) cell have been used for the first time as an interface between high-performance liquid chromatography (HPLC) and atomic fluorescence spectrometry (AFS) for selenium speciation. The newly designed ECVG cell of approximately 115 microL dead volume consists of a carbon fiber cathode and a platinum loop anode; the atomic hydrogen generated on the cathode was used to reduce selenium to vapor species for AFS determination. The noise was greatly reduced compared with that obtained by use of the UV-UV/TiO2 PCRD-KBH4-acid interface. The detection limits obtained for seleno-DL: -cystine (SeCys), selenite (Se(IV)), seleno-DL: -methionine (SeMet), and selenate (Se(VI)) were 2.1, 2.9, 4.3, and 3.5 ng mL(-1), respectively. The proposed method was successfully applied to the speciation of selenium in water-soluble extracts of garlic shoots cultured with different selenium species. The results obtained suggested that UV-UV/TiO2 PCRD-ECVG should be an effective interface between HPLC and AFS for the speciation of elements amenable to vapor generation, and is superior to methods involving KBH4.

Thallium release from acid mine drainages: Speciation in river and tap water from Valdicastello mining district (northwest Tuscany).

PubMed

Campanella, Beatrice; Casiot, Corinne; Onor, Massimo; Perotti, Martina; Petrini, Riccardo; Bramanti, Emilia

2017-08-15

In this work we present an advantageous method for the simultaneous separation and detection of Tl(I) and Tl(III) species through ion chromatography coupled with on-line inductively coupled plasma - mass spectrometry. Chromatographic separation between Tl(III) and Tl(I) was achieved in less than two minutes. The method was validated by recovery experiments on real samples, and by comparing the sum of the concentrations of individual Tl species with total thallium values obtained from continuous flow ICP-MS. The experimental procedure offers an accurate, sensitive and interference-free method for Tl speciation at trace levels in environmental samples. This allowed us to investigate the Tl speciation in acid mine drainages (AMD), surface waters and springs in a mining catchment in Valdicastello Carducci (Tuscany, Italy), where severe Tl contamination ad been evidenced previously. This study shows for the first time that Tl(III), in addition to Tl(I), is present in considerable amounts in water samples affected by acid mining outflow, raising the question of the origin of this thermodynamically unstable species. Copyright © 2017 Elsevier B.V. All rights reserved.

Speciation of hexavalent chromium in welding fumes interference by air oxidation of chromium.

PubMed

Zatka, V J

1985-06-01

The determination of various chromium species in welding fume normally involves digestion in a hot alkaline solution. This work confirms that Cr(III) can be oxidized to Cr(VI) during this digestion. However, only dissolved forms of Cr(III), such as the hydroxochromate(III) ion, [Cr(OH)4], are susceptible to oxidation under these conditions. The air oxidation of Cr(III) can be prevented by hydrolytic destabilization of the hydroxochromate(III) complex by the presence of magnesium hydroxide precipitate. The procedure has been used successfully in the determination of insoluble chromium(VI) in welding fumes. Excellent reproducibility is documented for soluble and insoluble chromium(VI) fractions in the analysis of a bulk sample of welding fume.

Interpreting the genomic landscape of speciation: a road map for finding barriers to gene flow.

PubMed

Ravinet, M; Faria, R; Butlin, R K; Galindo, J; Bierne, N; Rafajlović, M; Noor, M A F; Mehlig, B; Westram, A M

2017-08-01

Speciation, the evolution of reproductive isolation among populations, is continuous, complex, and involves multiple, interacting barriers. Until it is complete, the effects of this process vary along the genome and can lead to a heterogeneous genomic landscape with peaks and troughs of differentiation and divergence. When gene flow occurs during speciation, barriers restricting gene flow locally in the genome lead to patterns of heterogeneity. However, genomic heterogeneity can also be produced or modified by variation in factors such as background selection and selective sweeps, recombination and mutation rate variation, and heterogeneous gene density. Extracting the effects of gene flow, divergent selection and reproductive isolation from such modifying factors presents a major challenge to speciation genomics. We argue one of the principal aims of the field is to identify the barrier loci involved in limiting gene flow. We first summarize the expected signatures of selection at barrier loci, at the genomic regions linked to them and across the entire genome. We then discuss the modifying factors that complicate the interpretation of the observed genomic landscape. Finally, we end with a road map for future speciation research: a proposal for how to account for these modifying factors and to progress towards understanding the nature of barrier loci. Despite the difficulties of interpreting empirical data, we argue that the availability of promising technical and analytical methods will shed further light on the important roles that gene flow and divergent selection have in shaping the genomic landscape of speciation. © 2017 European Society For Evolutionary Biology. Journal of Evolutionary Biology © 2017 European Society For Evolutionary Biology.

Simultaneous Speciation of Arsenic, Selenium, and Chromium by HPLC-ICP-MS

USGS Publications Warehouse

Wolf, Ruth E.; Morman, Suzette A.; Morrison, Jean M.; Lamothe, Paul J.

2008-01-01

An adaptation of an analytical method developed for chromium speciation has been utilized for the simultaneous determination of As(III), As(V), Se(IV), Se(VI), Cr(III), and Cr(VI) species using high performance liquid chromatography (HPLC) separation with ICP-MS detection. Reduction of interferences for the determination of As, Se, and Cr by ICP-MS is a major consideration for this method. Toward this end, a Dynamic Reaction Cell (DRC) ICP-MS system was used to detect the species eluted from the chromatographic column. A variety of reaction cell gases and conditions may be utilized, and the advantages and limitations of the gases tested to date will be presented and discussed. The separation and detection of the As, Se, and Cr species of interest can be achieved using the same chromatographic conditions in less than 2 minutes by complexing the Cr(III) with EDTA prior to injection on the HPLC column. Practical aspects of simultaneous speciation analysis will be presented and discussed, including issues with HPLC sample vial contamination, standard and sample contamination, species stability, and considerations regarding sample collection and preservation methods. The results of testing to determine the method's robustness to common concomitant element and anion effects will also be discussed. Finally, results will be presented using the method for the analysis of a variety of environmental and geological samples including waters, soil leachates and simulated bio-fluid leachates.

Prediction of chemical speciation in stabilized/solidified wastes using a general chemical equilibrium model. Part 1: Chemical representation of cementitious binders

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, J.Y.; Batchelor, B.

1999-03-01

Chemical equilibrium models are useful to evaluate stabilized/solidified waste. A general equilibrium model, SOLTEQ, a modified version of MINTEQA2 for S/S, was applied to predict the chemical speciations in the stabilized/solidified waste form. A method was developed to prepare SOLTEQ input data that can chemically represent various stabilized/solidified binders. Taylor`s empirical model was used to describe partitioning of alkali ions. As a result, SOLTEQ could represent chemical speciation in pure binder systems such as ordinary Portland cement and ordinary Portland cement + fly ash. Moreover, SOLTEQ could reasonably describe the effects on the chemical speciation due to variations in water-to-cement,more » fly ash contents, and hydration times of various binder systems. However, this application of SOLTEQ was not accurate in predicting concentrations of Ca, Si, and SO{sub 4} ions, due to uncertainties in the CSH solubility model and K{sub sp} values of cement hydrates at high pH values.« less

Microcolumn-based speciation analysis of thallium in soil and green cabbage.

PubMed

Jia, Yanlong; Xiao, Tangfu; Sun, Jialong; Yang, Fei; Baveye, Philippe C

2018-07-15

Thallium (Tl) is a toxic trace metal, whose geochemical behavior and biological effects are closely controlled by its chemical speciation in the environment. However, little tends to be known about this speciation of Tl in soil and plant systems that directly affect the safety of food supplies. In this context, the objective of the present study was to elaborate an efficient method to separate and detect Tl(I) and Tl(III) species for soil and plant samples. This method involves the selective adsorption of Tl(I) on microcolumns filled with immobilized oxine, in the presence of DTPA (diethylenetriaminepentaacetic acid), followed by DTPA-enhanced ultrasonic and heating-induced extraction, coupled with ICP-MS detection. The method was characterized by a LOD of 0.037 μg/L for Tl(I) and 0.18 μg/L for Tl(III) in 10  mL samples. With this method, a second objective of the research was to assess the speciation of Tl in pot and field soils and in green cabbage crops. Experimental results suggest that DTPA extracted Tl was mainly present as Tl(I) in soils (>95%). Tl in hyperaccumulator plant green cabbage was also mainly present as Tl(I) (>90%). With respect to Tl uptake in plants, this study provides direct evidence that green cabbage mainly takes up Tl(I) from soil, and transports it into the aboveground organs. In soils, Tl(III) is reduced to Tl(I) even at the surface where the chemical environment promotes oxidation. This observation is conducive to understanding the mechanisms of Tl isotope fractionation in the soil-plant system. Based on geochemical fraction studies, the reducible fraction was the main source of Tl getting accumulated by plants. These results indicate that the improved analytical method presented in this study offers an economical, simple, fast, and sensitive approach for the separation of Tl species present in soils at trace levels. Copyright © 2018 Elsevier B.V. All rights reserved.

Trace metal speciation in natural waters: Computational vs. analytical

USGS Publications Warehouse

Nordstrom, D. Kirk

1996-01-01

Improvements in the field sampling, preservation, and determination of trace metals in natural waters have made many analyses more reliable and less affected by contamination. The speciation of trace metals, however, remains controversial. Chemical model speciation calculations do not necessarily agree with voltammetric, ion exchange, potentiometric, or other analytical speciation techniques. When metal-organic complexes are important, model calculations are not usually helpful and on-site analytical separations are essential. Many analytical speciation techniques have serious interferences and only work well for a limited subset of water types and compositions. A combined approach to the evaluation of speciation could greatly reduce these uncertainties. The approach proposed would be to (1) compare and contrast different analytical techniques with each other and with computed speciation, (2) compare computed trace metal speciation with reliable measurements of solubility, potentiometry, and mean activity coefficients, and (3) compare different model calculations with each other for the same set of water analyses, especially where supplementary data on speciation already exist. A comparison and critique of analytical with chemical model speciation for a range of water samples would delineate the useful range and limitations of these different approaches to speciation. Both model calculations and analytical determinations have useful and different constraints on the range of possible speciation such that they can provide much better insight into speciation when used together. Major discrepancies in the thermodynamic databases of speciation models can be evaluated with the aid of analytical speciation, and when the thermodynamic models are highly consistent and reliable, the sources of error in the analytical speciation can be evaluated. Major thermodynamic discrepancies also can be evaluated by simulating solubility and activity coefficient data and testing various chemical models for their range of applicability. Until a comparative approach such as this is taken, trace metal speciation will remain highly uncertain and controversial.

From Gene Trees to a Dated Allopolyploid Network: Insights from the Angiosperm Genus Viola (Violaceae)

PubMed Central

Marcussen, Thomas; Heier, Lise; Brysting, Anne K.; Oxelman, Bengt; Jakobsen, Kjetill S.

2015-01-01

Allopolyploidization accounts for a significant fraction of speciation events in many eukaryotic lineages. However, existing phylogenetic and dating methods require tree-like topologies and are unable to handle the network-like phylogenetic relationships of lineages containing allopolyploids. No explicit framework has so far been established for evaluating competing network topologies, and few attempts have been made to date phylogenetic networks. We used a four-step approach to generate a dated polyploid species network for the cosmopolitan angiosperm genus Viola L. (Violaceae Batch.). The genus contains ca 600 species and both recent (neo-) and more ancient (meso-) polyploid lineages distributed over 16 sections. First, we obtained DNA sequences of three low-copy nuclear genes and one chloroplast region, from 42 species representing all 16 sections. Second, we obtained fossil-calibrated chronograms for each nuclear gene marker. Third, we determined the most parsimonious multilabeled genome tree and its corresponding network, resolved at the section (not the species) level. Reconstructing the “correct” network for a set of polyploids depends on recovering all homoeologs, i.e., all subgenomes, in these polyploids. Assuming the presence of Viola subgenome lineages that were not detected by the nuclear gene phylogenies (“ghost subgenome lineages”) significantly reduced the number of inferred polyploidization events. We identified the most parsimonious network topology from a set of five competing scenarios differing in the interpretation of homoeolog extinctions and lineage sorting, based on (i) fewest possible ghost subgenome lineages, (ii) fewest possible polyploidization events, and (iii) least possible deviation from expected ploidy as inferred from available chromosome counts of the involved polyploid taxa. Finally, we estimated the homoploid and polyploid speciation times of the most parsimonious network. Homoploid speciation times were estimated by coalescent analysis of gene tree node ages. Polyploid speciation times were estimated by comparing branch lengths and speciation rates of lineages with and without ploidy shifts. Our analyses recognize Viola as an old genus (crown age 31 Ma) whose evolutionary history has been profoundly affected by allopolyploidy. Between 16 and 21 allopolyploidizations are necessary to explain the diversification of the 16 major lineages (sections) of Viola, suggesting that allopolyploidy has accounted for a high percentage—between 67% and 88%—of the speciation events at this level. The theoretical and methodological approaches presented here for (i) constructing networks and (ii) dating speciation events within a network, have general applicability for phylogenetic studies of groups where allopolyploidization has occurred. They make explicit use of a hitherto underexplored source of ploidy information from chromosome counts to help resolve phylogenetic cases where incomplete sequence data hampers network inference. Importantly, the coalescent-based method used herein circumvents the assumption of tree-like evolution required by most techniques for dating speciation events. PMID:25281848

Detecting Hidden Diversification Shifts in Models of Trait-Dependent Speciation and Extinction.

PubMed

Beaulieu, Jeremy M; O'Meara, Brian C

2016-07-01

The distribution of diversity can vary considerably from clade to clade. Attempts to understand these patterns often employ state-dependent speciation and extinction models to determine whether the evolution of a particular novel trait has increased speciation rates and/or decreased extinction rates. It is still unclear, however, whether these models are uncovering important drivers of diversification, or whether they are simply pointing to more complex patterns involving many unmeasured and co-distributed factors. Here we describe an extension to the popular state-dependent speciation and extinction models that specifically accounts for the presence of unmeasured factors that could impact diversification rates estimated for the states of any observed trait, addressing at least one major criticism of BiSSE (Binary State Speciation and Extinction) methods. Specifically, our model, which we refer to as HiSSE (Hidden State Speciation and Extinction), assumes that related to each observed state in the model are "hidden" states that exhibit potentially distinct diversification dynamics and transition rates than the observed states in isolation. We also demonstrate how our model can be used as character-independent diversification models that allow for a complex diversification process that is independent of the evolution of a character. Under rigorous simulation tests and when applied to empirical data, we find that HiSSE performs reasonably well, and can at least detect net diversification rate differences between observed and hidden states and detect when diversification rate differences do not correlate with the observed states. We discuss the remaining issues with state-dependent speciation and extinction models in general, and the important ways in which HiSSE provides a more nuanced understanding of trait-dependent diversification. © The Author(s) 2016. Published by Oxford University Press, on behalf of the Society of Systematic Biologists. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

[Study on arsenic speciation changes in crude and processed traditional Chinese medicines by HPLC-ICP-MS].

PubMed

Jin, Peng-fei; Wu, Xue-jun; Zou, Ding; Kuang, Yong-mei; Hu, Xin; Jiang, Wen-qing; Sun, Chun-hua

2011-03-01

A HPLC-ICP-MS method for simultaneous determination of As(III), As(V), MMA and DMA in traditional Chinese medicines (TCMs) was established, and the contents of As(III), As(V), MMA and DMA in a TCM with high total arsenic content (Cordyceps) and 5 crude and processed TCMs (Radix Astragali, Radix et Rhizoma Rhei, Radix Scutellariae, Radix Polygoni Multiflori and Radix Rehmanniae) were determined and analyzed. The method validation indicated that the correlative coefficients (r) for all speciations were bigger than 0.9984; the limits of quantitation (LOQ) were from 0.8 to 1.0 microg x L(-1); the reproducibility and stability were satisfactory with all RSDs less than 10%; the spiked recoveries ranged from 82.40% to 119.5%. The results of samples analysis showed that the inorganic arsenic (As(III) and As(V)) was the dominating speciation in the tested TCMs; MMA and DMA were not found in all plant resourced TCMs, but MMA was found in Cordyceps; all the tested TCMs indicated a content increasing of inorganic arsenic after processing.

Determination of arsenite, arsenate, monomethylarsonic acid and dimethylarsinic acid in cereals by hydride generation atomic fluorescence spectrometry

NASA Astrophysics Data System (ADS)

Matos Reyes, M. N.; Cervera, M. L.; Campos, R. C.; de la Guardia, M.

2007-09-01

A fast, sensitive and simple non-chromatographic analytical method was developed for the speciation analysis of toxic arsenic species in cereal samples, namely rice and wheat semolina. An ultrasound-assisted extraction of the toxic arsenic species was performed with 1 mol L - 1 H 3PO 4 and 0.1% (m/v) Triton XT-114. After extraction, As(III), As(V), dimethylarsinic acid (DMA) and monomethylarsonic acid (MMA) concentrations were determined by hydride generation atomic fluorescence spectrometry using a series of proportional equations corresponding to four different experimental reduction conditions. The detection limits of the method were 1.3, 0.9, 1.5 and 0.6 ng g - 1 for As(III), As(V), DMA and MMA, respectively, expressed in terms of sample dry weight. Recoveries were always greater than 90%, and no species interconversion occurred. The speciation analysis of a rice flour reference material certified for total arsenic led to coherent results, which were also in agreement with other speciation studies made on the same certified reference material.

Ultrasound-assisted ionic liquid dispersive liquid-liquid microextraction combined with graphite furnace atomic absorption spectrometric for selenium speciation in foods and beverages.

PubMed

Tuzen, Mustafa; Pekiner, Ozlem Zeynep

2015-12-01

A rapid and environmentally friendly ultrasound assisted ionic liquid dispersive liquid liquid microextraction (USA-IL-DLLME) was developed for the speciation of inorganic selenium in beverages and total selenium in food samples by using graphite furnace atomic absorption spectrometry. Some analytical parameters including pH, amount of complexing agent, extraction time, volume of ionic liquid, sample volume, etc. were optimized. Matrix effects were also investigated. Enhancement factor (EF) and limit of detection (LOD) for Se(IV) were found to be 150 and 12 ng L(-1), respectively. The relative standard deviation (RSD) was found 4.2%. The accuracy of the method was confirmed with analysis of LGC 6010 Hard drinking water and NIST SRM 1573a Tomato leaves standard reference materials. Optimized method was applied to ice tea, soda and mineral water for the speciation of Se(IV) and Se(VI) and some food samples including beer, cow's milk, red wine, mixed fruit juice, date, apple, orange, grapefruit, egg and honey for the determination of total selenium. Copyright © 2015 Elsevier Ltd. All rights reserved.

Visualizing speciation in artificial cichlid fish.

PubMed

Clement, Ross

2006-01-01

The Cichlid Speciation Project (CSP) is an ALife simulation system for investigating open problems in the speciation of African cichlid fish. The CSP can be used to perform a wide range of experiments that show that speciation is a natural consequence of certain biological systems. A visualization system capable of extracting the history of speciation from low-level trace data and creating a phylogenetic tree has been implemented. Unlike previous approaches, this visualization system presents a concrete trace of speciation, rather than a summary of low-level information from which the viewer can make subjective decisions on how speciation progressed. The phylogenetic trees are a more objective visualization of speciation, and enable automated collection and summarization of the results of experiments. The visualization system is used to create a phylogenetic tree from an experiment that models sympatric speciation.

Review on physical and chemical characterizations of contaminated sediments from urban stormwater infiltration basins within the framework of the French observatory for urban hydrology (SOERE URBIS).

PubMed

El-Mufleh, Amelène; Béchet, Béatrice; Ruban, Véronique; Legret, Michel; Clozel, Blandine; Barraud, Sylvie; Gonzalez-Merchan, Carolina; Bedell, Jean-Philippe; Delolme, Cécile

2014-04-01

Urban stormwater infiltration basins are designed to hold runoff from impervious surfaces and allow the settling of sediments and associated pollutants. However concerns have been expressed about the environmental impacts that may be exerted by the trapped pollutants on groundwater, soils and ecosystems. In this context, sediment characterization represents a key issue for local authorities in terms of management strategies. During the last two decades, several studies were launched including either physical or chemical characterization of stormwater sediments but without real synthesis of data and methods used. Consequently, there is an important need for reviewing the current experimental techniques devoted to the physico-chemical characterization of sediment. The review is based on the outcomes of two experimental sites for which long term monitoring and data collection have been done: the Cheviré basin (near Nantes) and the Django Reinhardt basin (near Lyon). The authors summarize the studies dealing with bulk properties, pollutant contents, their potential mobility and speciation. This paper aims at promoting the significant progresses that were made through a multidisciplinary approach involving multi-scaled and combined experimental techniques.

EPA’s SPECIATE 4.4 Database:Development and Uses

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency's (EPA)repository of volatile organic gas and particulate matter (PM) speciation profiles for air pollution sources. EPA released SPECIATE 4.4 in early 2014 and, in total, the SPECIATE 4.4 database includes 5,728 PM, VOC, total...

EPA’s SPECIATE 4.4 Database: Development and Uses

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency's (EPA)repository of volatile organic gas and particulate matter (PM) speciation profiles for air pollution sources. EPA released SPECIATE 4.4 in early 2014 and, in total, the SPECIATE 4.4 database includes 5,728 PM, VOC, total...

Evaluation of speciated VOC emission factors for Air Force hush houses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sullivan, P.D.; Stevens, D.K.

1997-12-31

Data published in: ``Engine and Hush House Emissions from a TF30-P109 Jet Engine Tested at Cannon Air Force Base, NM`` by Radian Corporation and ``Aircraft Emissions. Characterization: TF41-A2, TF30-P103 , and TF30-P109 Engines`` by Battelle are reviewed and compared. Specifically CO, NO{sub x}, and VOC emission factors using EPA Method 19 are addressed, with comparisons between JP-4 and JP-8 jet fuels. CO and NO{sub x} emissions for JP-4 and JP-8 jet fuels were found to be essentially the same. VOC emission data exhibited high variability. Problems inherent in speciated VOC emission testing are discussed. A limiting of speciated VOC emissionmore » testing, with emission factor estimation based on fuel content is proposed.« less

Appropriate sampling strategy and analytical methodology to address contamination by industry. Part 2: Geochemistry and speciation analysis

NASA Astrophysics Data System (ADS)

Shtiza, Aurela; Swennen, Rudy

2011-03-01

The degree of contamination in soils, sediments and dusts can be assessed based on knowledge of a variety of factors, such as industrialization, type of contaminants, deposition conditions, contamination-control techniques, along with the characteristics of the recipient environmental compartments, which include pathways for contamination transport, depth of infiltration, and degree of groundwater contamination. The impact of contaminants also depends on the quantity, mobility and speciation of contaminants/wastes as well as on the sensitivity of the recipient compartments. With sufficient knowledge of these factors, a number of conclusions can be drawn concerning the status of contamination in industrialized areas. This literature review aims to scrutinize some of the methods used to analyse the occurrence, speciation, mobility, bioavailability and likely the toxic effects of contaminants in the environment.

Chromium(III)-imprinted silica gel for speciation analysis of chromium in environmental water samples with ICP-MS detection.

PubMed

Zhang, Nan; Suleiman, Jibrin Sabo; He, Man; Hu, Bin

2008-04-15

A new chromium(III)-imprinted 3-(2-aminoethylamino) propyltrimethoxysilane (AAPTS)-functionalized silica gel sorbent was synthesized by a surface imprinting technique and was employed as a selective solid-phase extraction material for speciation analysis of chromium in environmental water samples prior to its determination by inductively coupled plasma mass spectrometry (ICP-MS). The prepared Cr(III)-imprinted silica gel shows the selectivity coefficient of more than 700 for Cr(III) in the presence of Mn(II). The static adsorption capacity of the ion-imprinted and non-imprinted sorbent for Cr(III) were 30.5 mg g(-1) and 13.4 mg g(-1). It was also found that Cr(VI) could be adsorbed at low pH by the prepared imprinted silica gel, and this finding makes it feasible to enrich and determine Cr(VI) at low pH without adding reducing reagents. The imprinted silica gel sorbent offered a fast kinetics for the adsorption and desorption of both chromium species. Under the optimized conditions, the detection limits of 4.43 pg mL(-1) and 8.30 pg mL(-1) with the relative standard deviations (R.S.D.s) of 4.44% and 4.41% (C=0.5 ng mL(-1), n=7) for Cr(III) and Cr(VI) were obtained, respectively. The proposed method was successfully applied to the speciation of trace chromium in environmental water samples. To validate the proposed method, two certified reference materials were analyzed and the determined values were in a good agreement with the certified values. The developed method is rapid, selective, sensitive and applicable for the speciation of trace chromium in environmental water samples.

US EPA's SPECIATE 4.4 Database: Development and Uses

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency’s (EPA) repository of volatile organic gas and particulate matter (PM) speciation profiles of air pollution sources. EPA released SPECIATE 4.4 in early 2014 and, in total, the SPECIATE 4.4 database includes 5,728 PM, volatile o...

EPA’s SPECIATE 4.4 Database: Bridging Data Sources and Data Users

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency's (EPA)repository of volatile organic gas and particulate matter (PM) speciation profiles for air pollution sources. EPA released SPECIATE 4.4 in early 2014 and, in total, the SPECIATE 4.4 database includes 5,728 PM, VOC, total...

40 CFR 58.10 - Annual monitoring network plan and periodic network assessment.

Code of Federal Regulations, 2012 CFR

2012-07-01

... part of SLAMS, NCore stations, STN stations, State speciation stations, SPM stations, and/or, in... analysis method(s) for each measured parameter. (4) The operating schedules for each monitor. (5) Any...

40 CFR 58.10 - Annual monitoring network plan and periodic network assessment.

Code of Federal Regulations, 2013 CFR

2013-07-01

... part of SLAMS, NCore stations, STN stations, State speciation stations, SPM stations, and/or, in... and analysis method(s) for each measured parameter. (4) The operating schedules for each monitor. (5...

40 CFR 58.10 - Annual monitoring network plan and periodic network assessment.

Code of Federal Regulations, 2014 CFR

2014-07-01

... part of SLAMS, NCore stations, STN stations, State speciation stations, SPM stations, and/or, in... and analysis method(s) for each measured parameter. (4) The operating schedules for each monitor. (5...

Toward the use of surface modified activated carbon in speciation: selective preconcentration of selenite and selenate in environmental waters.

PubMed

Tsoi, Yeuk-Ki; Leung, Kelvin Sze-Yin

2011-04-22

This paper describes a novel application of tetrabutylammonium hydroxide-modified activated carbon (AC-TBAH) to the speciation of ultra-trace Se(IV) and Se(VI) using LC-ICP-DRC-MS. The anion exchange functionality was immobilized onto the AC surface enables selective preconcentration of inorganic Se anions in a wide range of working pHs. Simultaneous retention and elution of both analytes, followed by subsequent analysis with LC-ICP-DRC-MS, allows to accomplish speciation analysis in natural samples without complicated redox pre-treatment. The laboratory-made column of immobilized AC (0.4 g of sorbent packed in a 6 mL syringe barrel) has achieved analyte enrichment factors of 76 and 93, respectively, for Se(IV) and Se(VI), thus proving its superior preconcentration efficiency and selectivity over common AC. The considerable enhancement in sensitivity achieved by using the preconcentration column has improved the method's detection limits to 1.9-2.2 ng L(-1), which is a 100-fold improvement compared with direct injection. The analyte recoveries from heavily polluted river matrix were between 95.3 and 107.7% with less than 5.0% RSD. The robustness of the preconcentration and speciation method was validated by analysis of natural waters collected from rivers and reservoirs in Hong Kong. The modified AC material is hence presented as a low-cost yet robust substitute for conventional anion exchange resins for routine applications. Copyright © 2011 Elsevier B.V. All rights reserved.

Micro and bulk analysis of prostate tissues classified as hyperplasia

NASA Astrophysics Data System (ADS)

Kwiatek, W. M.; Banaś, A.; Banaś, K.; Cinque, G.; Dyduch, G.; Falkenberg, G.; Kisiel, A.; Marcelli, A.; Podgórczyk, M.

2007-07-01

BPH (Benign Prostatic Hyperplasia) is the most common benign neoplasm (non cancerous enlargement of the prostate gland), whose prevalence increases with age. The gland, when increased in size, exerts pressure on the urethra, causing obstruction to urine flow. The latter may result in severe urinary tract and kidney conditions. In this work prostate samples from patients diagnosed with BPH were analyzed using synchrotron radiation. Micro-analysis of the hyperplastic samples was carried out on the L-beam line at HASYLAB, DESY (Germany), while bulk analysis on selected samples was performed at the DRX2 beamline at LNF, Frascati (Italy). Microanalysis with a mono-energetic beam 15 μm in diameter confirmed that concentrations of certain elements, such as S, Mn, Cu, Fe and Zn, are good indicators of pathological disorders in prostate tissue that may be considered effective tracers of developing compliant. The concentrations of Mn, Cu, Fe and Zn are higher in hyperplastic tissues, as compared to normal ones, while for sulphur the opposite is observed. Additionally, Fe and S K-edge XANES (X-ray Absorption Near Edge Structure) spectroscopy experiments were carried out in order to determine the chemical speciation of these elements in our samples.

Selective determination of heavy metals (Cd, Pb, Cr) speciation forms from hortic anthrosols

NASA Astrophysics Data System (ADS)

Bulgariu, Dumitru; Bulgariu, Laura; Filipov, Feodor; Astefanei, Dan; Stoleru, Vasile

2010-05-01

In soils from glass houses, the speciation and inter-phases distribution processes of heavy metals have a particular dynamic, different in comparison with those from non-protected soils. The predominant distribution forms of heavy metals in such soils types are: complexes with low mass organic molecules, organic-mineral complexes, complexes with inorganic ligands (hydroxide-complexes, carbonate-complexes, sulphate-complexes, etc.) and basic salts. All of these have high stabilities in conditions of soils from glass houses, and in consequence, the separation and determination of speciation forms (which is directly connected with biodisponibility of heavy metals) by usual methods id very difficult and has a high uncertain degree. In this study is presented an original method for the selective separation and differentiation of speciation forms of heavy metals from glass houses soils, which is based by the combination of solid-liquid sequential extraction (SPE) with the extraction in aqueous polymer-inorganic salt two-phase systems (ABS). The soil samples used for this study have been sampled from three different locations (glass houses from Iasi, Barlad and Bacau - Romania) where the vegetables cultivation have been performed by three different technologies. In this way was estimated the applicability and the analytical limits of method proposed by as, in function of the chemical-mineralogical and physical-chemical characteristics of soils. As heavy metals have been studied cadmium, lead and chromium, all being known for their high toxicity. The procedure used for the selective separation and differentiation of speciation forms of heavy metals from glass houses soils has two main steps: (i) non-destructive separation of chemical-mineralogical associations and aggregates from soils samples - for this the separation method with heavy liquids (bromophorme) and isodynamic magnetic method have been used; (ii) sequential extraction of heavy metals from soil fractions separated in the first step, by using combined SPE-ABS procedure. For the preparation of combined extraction systems was used polyethylene glycol (with different molecular mass: 2000, 4000 and 8000). As phase-forming inorganic salts and as selective extracting agents we have used different usual inorganic reagents. The type and concentration of phase-forming salts have been selected in function of, both nature of extracted heavy metals and chemical-mineralogical characteristics of soil samples. The experimental parameters investigated in this study are: molecular mass of polyethylene glycol and the concentration of polymeric solutions, nature and concentration of phase-forming salts, nature and concentration of extracting agents, pH in extraction system phase, type of extracted heavy metals, type of speciation forms of heavy metals and their concentrations. All these factors can influence significantly the efficiency and the selectivity of separation process. The experimental results have indicate that the combined SPE-ABS extraction systems have better separation efficiency, in comparison with traditional SPE systems and ca realized a accurate discrimination between speciation forms of heavy metals from soils. Under these conditions, the estimation of inter-phases distribution and biodisponibility of heavy metals has a high precision. On the other hand, when the combined SPE-ABS systems are used, the concomitant extraction of the elements from the same geochemical association with studied heavy metals (inevitable phenomena in case of separation by SPE procedures) is significant diminished. This increases the separation selectivity and facilitated the more accurate determination of speciation forms concentration. By adequate selection of extraction conditions can be realized the selective separation of organic-mineral complexes, which will permit to perform detailed studies about the structure and chemical composition of these. Acknowledgments The authors would like to acknowledge the financial support from Romanian Ministry of Education and Research (Project PNCDI 2-D5 no. 51045/07 and project PNCDI 2 - D5 no. 52-141 / 2008).

Invasive species and biodiversity crises: testing the link in the late devonian.

PubMed

Stigall, Alycia L

2010-12-29

During the Late Devonian Biodiversity Crisis, the primary driver of biodiversity decline was the dramatic reduction in speciation rates, not elevated extinction rates; however, the causes of speciation decline have been previously unstudied. Speciation, the formation of new species from ancestral populations, occurs by two primary allopatric mechanisms: vicariance, where the ancestral population is passively divided into two large subpopulations that later diverge and form two daughter species, and dispersal, in which a small subset of the ancestral population actively migrates then diverges to form a new species. Studies of modern and fossil clades typically document speciation by vicariance in much higher frequencies than speciation by dispersal. To assess the mechanism behind Late Devonian speciation reduction, speciation rates were calculated within stratigraphically constrained species-level phylogenetic hypotheses for three representative clades and mode of speciation at cladogenetic events was assessed across four clades in three phyla: Arthropoda, Brachiopoda, and Mollusca. In all cases, Devonian taxa exhibited a congruent reduction in speciation rate between the Middle Devonian pre-crisis interval and the Late Devonian crisis interval. Furthermore, speciation via vicariance is almost entirely absent during the crisis interval; most episodes of speciation during this time were due to dispersal. The shutdown of speciation by vicariance during this interval was related to widespread interbasinal species invasions. The lack of Late Devonian vicariance is diametrically opposed to the pattern observed in other geologic intervals, which suggests the loss of vicariant speciation attributable to species invasions during the Late Devonian was a causal factor in the biodiversity crisis. Similarly, modern ecosystems, in which invasive species are rampant, may be expected to exhibit similar shutdown of speciation by vicariance as an outcome of the modern biodiversity crisis.

Phosphate and phytate adsorption and precipitation on ferrihydrite surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Xiaoming; Hu, Yongfeng; Tang, Yadong

Phosphorous (P) sorption on mineral surfaces largely controls P mobility and bioavailability, hence its pollution potential, but the sorption speciation and mechanism remain poorly understood. In this study, we have identified and quantified the speciation of both phosphate and phytate sorbed on ferrihydrite with various P loadings at pH 3–8 using differential atomic pair distribution function (d-PDF) analysis, synchrotron-based X-ray diffraction (XRD), and P and Fe K-edge X-ray absorption near edge structure (XANES) and attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. With increasing P sorption loading for both phosphate and phytate, the sorption mechanism transits from bidentate-binuclear surface complexation tomore » unidentified ternary complexation and to precipitation of amorphous FePO 4 and amorphous Fe-phytate. At a given P sorption loading, phosphate precipitates more readily than phytate. Both phosphate and phytate promote ferrihydrite dissolution with phytate more intensively, but the dissolved FeIII concentration in the bulk solution is low because the majority of the released Fe III precipitate with the anions. Results also show that amorphous FePO 4 and amorphous Fe-phytate have similar PO 4 local coordination environment. In conclusion, these new insights into the P surface complexation and precipitation, and the ligand-promoted dissolution behavior improve our understanding of P fate in soils, aquatic environment and water treatment systems as mediated by mineral-water interfacial reactions.« less

Phosphate and phytate adsorption and precipitation on ferrihydrite surfaces

DOE PAGES

Wang, Xiaoming; Hu, Yongfeng; Tang, Yadong; ...

2017-09-26

Phosphorous (P) sorption on mineral surfaces largely controls P mobility and bioavailability, hence its pollution potential, but the sorption speciation and mechanism remain poorly understood. In this study, we have identified and quantified the speciation of both phosphate and phytate sorbed on ferrihydrite with various P loadings at pH 3–8 using differential atomic pair distribution function (d-PDF) analysis, synchrotron-based X-ray diffraction (XRD), and P and Fe K-edge X-ray absorption near edge structure (XANES) and attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. With increasing P sorption loading for both phosphate and phytate, the sorption mechanism transits from bidentate-binuclear surface complexation tomore » unidentified ternary complexation and to precipitation of amorphous FePO 4 and amorphous Fe-phytate. At a given P sorption loading, phosphate precipitates more readily than phytate. Both phosphate and phytate promote ferrihydrite dissolution with phytate more intensively, but the dissolved FeIII concentration in the bulk solution is low because the majority of the released Fe III precipitate with the anions. Results also show that amorphous FePO 4 and amorphous Fe-phytate have similar PO 4 local coordination environment. In conclusion, these new insights into the P surface complexation and precipitation, and the ligand-promoted dissolution behavior improve our understanding of P fate in soils, aquatic environment and water treatment systems as mediated by mineral-water interfacial reactions.« less

Iron speciation and isotope fractionation during silicate weathering and soil formation in an alpine glacier forefield chronosequence

NASA Astrophysics Data System (ADS)

Kiczka, Mirjam; Wiederhold, Jan G.; Frommer, Jakob; Voegelin, Andreas; Kraemer, Stephan M.; Bourdon, Bernard; Kretzschmar, Ruben

2011-10-01

The chemical weathering of primary Fe-bearing minerals, such as biotite and chlorite, is a key step of soil formation and an important nutrient source for the establishment of plant and microbial life. The understanding of the relevant processes and the associated Fe isotope fractionation is therefore of major importance for the further development of stable Fe isotopes as a tracer of the biogeochemical Fe cycle in terrestrial environments. We investigated the Fe mineral transformations and associated Fe isotope fractionation in a soil chronosequence of the Swiss Alps covering 150 years of soil formation on granite. For this purpose, we combined for the first time stable Fe isotope analyses with synchrotron-based Fe-EXAFS spectroscopy, which allowed us to interpret changes in Fe isotopic composition of bulk soils, size fractions, and chemically separated Fe pools over time in terms of weathering processes. Bulk soils and rocks exhibited constant isotopic compositions along the chronosequence, whereas soil Fe pools in grain size fractions spanned a range of 0.4‰ in δ 56Fe. The clay fractions (<2 μm), in which newly formed Fe(III)-(hydr)oxides contributed up to 50% of the total Fe, were significantly enriched in light Fe isotopes, whereas the isotopic composition of silt and sand fractions, containing most of the soil Fe, remained in the range described by biotite/chlorite samples and bulk soils. Iron pools separated by a sequential extraction procedure covered a range of 0.8‰ in δ 56Fe. For all soils the lightest isotopic composition was observed in a 1 M NH 2OH-HCl-25% acetic acid extract, targeting poorly-crystalline Fe(III)-(hydr)oxides, compared with easily leachable Fe in primary phyllosilicates (0.5 M HCl extract) and Fe in residual silicates. The combination of the Fe isotope measurements with the speciation data obtained by Fe-EXAFS spectroscopy permitted to quantitatively relate the different isotope pools forming in the soils to the mineral weathering reactions which have taken place at the field site. A kinetic isotope effect during the Fe detachment from the phyllosilicates was identified as the dominant fractionation mechanism in young weathering environments, controlling not only the light isotope signature of secondary Fe(III)-(hydr)oxides but also significantly contributing to the isotope signature of plants. The present study further revealed that this kinetic fractionation effect can persist over considerable reaction advance during chemical weathering in field systems and is not only an initial transient phenomenon.

Hydrogen speciation in hydrated layers on nuclear waste glass

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aines, R.D.; Weed, H.C.; Bates, J.K.

1987-01-15

The hydration of an outer layer on nuclear waste glasses is known to occur during leaching, but the actual speciation of hydrogen (as water or hydroxyl groups) in these layers has not been determined. As part of the Nevada Nuclear Waste Storage Investigations Project, we have used infrared spectroscopy to determine hydrogen speciations in three nuclear waste glass compositions (SRL-131 & 165, and PNL 76-68), which were leached at 90{sup 0}C (all glasses) or hydrated in a vapor-saturated atmosphere at 202{sup 0}C (SRL-131 only). Hydroxyl groups were found in the surface layers of all the glasses. Molecular water was foundmore » in the surface of SRL-131 and PNL 76-68 glasses that had been leached for several months in deionized water, and in the vapor-hydrated sample. The water/hydroxyl ratio increases with increasing reaction time; molecular water makes up most of the hydrogen in the thick reaction layers on vapor-phase hydrated glass while only hydroxyl occurs in the least reacted samples. Using the known molar absorptivities of water and hydroxyl in silica-rich glass the vapor-phase layer contained 4.8 moles/liter of molecular water, and 0.6 moles water in the form hydroxyl. A 15 {mu}m layer on SRL-131 glass formed by leaching at 90{sup 0}C contained a total of 4.9 moles/liter of water, 2/3 of which was as hydroxyl. The unreacted bulk glass contains about 0.018 moles/liter water, all as hydroxyl. The amount of hydrogen added to the SRL-131 glass was about 70% of the original Na + Li content, not the 300% that would result from alkali=hydronium ion interdiffusion. If all the hydrogen is then assumed to be added as the result of alkali-H{sup +} interdiffusion, the molecular water observed may have formed from condensation of the original hydroxyl groups.« less

Theoretical estimation of equilibrium sulfur isotope fractionations among aqueous sulfite species: Implications for isotope models of microbial sulfate reduction

NASA Astrophysics Data System (ADS)

Eldridge, D. L.; Farquhar, J.; Guo, W.

2015-12-01

Sulfite (sensu lato), an intermediate in a variety sulfur redox processes, plays a particularly important role in microbial sulfate reduction. It exists intracellularly as multiple species between sets of enzymatic reactions that transform sulfate to sulfide, with the exact speciation depending on pH, T, and ionic strength. However, the complex speciation of sulfite is ignored in current isotope partitioning models of microbial sulfate reduction and simplified solely to the pyramidal SO32- (sulfite sensu stricto), due to a lack of appropriate constraints. We theoretically estimated the equilibrium sulfur isotope fractionations (33S/32S, 34S/32S, 36S/32S) among all documented sulfite species in aqueous solution, including sulfite (SO32-), bisulfite isomers and dimers ((HS)O3-, (HO)SO2-, S2O52-), and SO2(aq), through first principles quantum mechanical calculations. The calculations were performed at B3LYP/6-31+G(d,p) level using cluster models with 30-40 water molecules surrounding the solute. Our calculated equilibrium fractionation factors compare well to the available experimental constraints and suggest that the minor and often-ignored tetrahedral (HS)O3- isomer of bisulfite strongly influences isotope partitioning behavior in the sulfite system under most environmentally relevant conditions, particularly fractionation magnitudes and unusual temperature dependence. For example, we predict that sulfur isotope fractionation between sulfite and bulk bisulfite in solution should have an apparent inverse temperature dependence due to the influence of (HS)O3- and its increased stability at higher temperatures. Our findings highlight the need to appropriately account for speciation/isomerization of sulfur species in sulfur isotope studies. We will also present similar calculation results of other aqueous sulfur compounds (e.g., H2S/HS-, SO42-, S2O32-, S3O62-, and poorly documented SO22- species), and discuss the implication of our results for microbial sulfate reduction models and other sulfur-redox processes in nature.

Magnetic solid-phase extraction combined with graphite furnace atomic absorption spectrometry for speciation of Cr(III) and Cr(VI) in environmental waters.

PubMed

Jiang, Hong-mei; Yang, Ting; Wang, Yan-hong; Lian, Hong-zhen; Hu, Xin

2013-11-15

A new approach of magnetic solid phase extraction (MSPE) coupled with graphite furnace atomic absorption spectrometry (GFAAS) has been developed for the speciation of Cr(III) and Cr(VI) using zincon-immobilized silica-coated magnetic Fe3O4 nanoparticles (Zincon-Si-MNPs) as the MSPE absorbent. Cr(III) was quantitatively reserved on the absorbent at pH 9.1 while total Cr was reserved at pH 6.5. The absorbed Cr species were eluted by using 2 mol/L HCl and detected by GFAAS. The concentration of Cr(VI) could be calculated by subtracting Cr(III) from total Cr. All the parameters affecting the separation and extraction efficiency of Cr species such as pH, extraction time, concentration and volume of eluent, sample volume and influence of co-existing ions were systematically examined and the optimized conditions were established accordingly. The detection limit (LOD) of the method was 0.016 and 0.011 ng mL(-1) for Cr(III) and Cr(VI), respectively, with the enrichment factor of 100 and 150. The precisions of this method (Relative standard deviation, RSD, n=7) for Cr(III) and Cr(VI) at 0.1 ng mL(-1) were 6.0% and 6.2%, respectively. In order to validate the proposed method, a certified reference material of environmental water was analyzed, and the result of Cr speciation was in good agreement with the certified value. This MSPE-GFAAS method has been successfully applied for the speciation of Cr(III) and Cr(VI) in lake and tap waters with the recoveries of 88-109% for the spiked samples. Moreover, the MSPE separation mechanism of Cr(III) and Cr(VI) based on their adsorption-desorption on Zincon-Si-MNPs has been explained through various spectroscopic characterization. © 2013 Elsevier B.V. All rights reserved.

Use of ion-pairing reagent for improving iodine speciation analysis in seaweed by pressure-driven capillary electrophoresis and ultraviolet detection.

PubMed

Sun, Jiannan; Wang, Dan; Cheng, Heyong; Liu, Jinhua; Wang, Yuanchao; Xu, Zigang

2015-01-30

This study achieved resolution improvement for iodine speciation in the presence of an ion-pairing reagent by a pressure-driven capillary electrophoresis (CE) system. Addition of 0.01mM tetrabutyl ammonium hydroxide (TBAH) as the ion-pairing reagent into the electrophoretic buffer resulted in the complete separation of four iodine species (I(-), IO3(-), mono-iodothyrosine-MIT and di-iodothyrosine-DIT), because of the electrostatic interaction between TBAH and the negatively charged analytes. A +16kV separation voltage was applied along the separation capillary (50μm i.d., 80cm total and 60cm effective) with the inlet grounded. The detection wavelength was fixed at 210nm, and the pressure-driven flow rate was set at 0.12mLmin(-1) with an injected volume of 2μL. The optimal electrolyte consisted of 2mM borate, 2mM TBAH and 80% methanol with pH adjusted to 8.5. Baseline separation of iodine species was achieved within 7min. The detection limits for I(-), IO3(-), MIT and DIT were 0.052, 0.040, 0.032 and 0.025mgL(-1), respectively. The relative standard deviations of peak heights and areas were all below 3% for 5mgL(-1) and 5% for 1mgL(-1). Application of the proposed method was demonstrated by speciation analysis of iodine in two seaweed samples. The developed method offered satisfactory recoveries in the 91-99% range and good precisions (<5%). Good agreement between the determined values by the proposed CE method and the HPLC-ICP-MS method was also obtained. All results proved its great potential in routine analysis of iodine speciation in environmental, food and biological samples. Copyright © 2014 Elsevier B.V. All rights reserved.

Chromium speciation in environmental samples using a solid phase spectrophotometric method.

PubMed

Amin, Alaa S; Kassem, Mohammed A

2012-10-01

A solid phase extraction technique is proposed for preconcentration and speciation of chromium in natural waters using spectrophotometric analysis. The procedure is based on sorption of chromium(III) as 4-(2-benzothiazolylazo)2,2'-biphenyldiol complex on dextran-type anion-exchange gel (Sephadex DEAE A-25). After reduction of Cr(VI) by 0.5 ml of 96% concentrated H(2)SO(4) and ethanol, the system was applied to the total chromium. The concentration of Cr(VI) was calculated as the difference between the total Cr and the Cr(III) content. The influences of some analytical parameters such as: pH of the aqueous solution, amounts of 4-(2-benzothiazolylazo)2,2'-biphenyldiol (BTABD), and sample volumes were investigated. The absorbance of the gel, at 628 and 750 nm, packed in a 1.0 mm cell, is measured directly. The molar absorptivities were found to be 2.11×10(7) and 3.90×10(7) L mol(-1)cm(-1) for 500 and 1000 ml, respectively. Calibration is linear over the range 0.05-1.45 μg L(-1) with RSD of <1.85% (n=8.0). Using 35 mg exchanger, the detection and quantification limits were 13 and 44 ng L(-1) for 500 ml sample, whereas for 1000 ml sample were 8.0 and 27 ng L(-1), respectively. Increasing the sample volume can enhance the sensitivity. No considerable interferences have been observed from other investigated anions and cations on the chromium speciation. The proposed method was applied to the speciation of chromium in natural waters and total chromium preconcentration in microwave digested tobacco, coffee, tea, and soil samples. The results were simultaneously compared with those obtained using an ET AAS method, whereby the validity of the method has been tested. Copyright © 2012 Elsevier B.V. All rights reserved.

SPECIATION OF ORGANICS IN WATER

EPA Science Inventory

We describe herein a method for determining constants for simultaneously occurring, site-specific "microequilibria" (as with tautomers) for organics in water. The method is based in part on modeling temperature-variant Raman spectra according to the van't Hoff equation....

Bio-metals imaging and speciation in cells using proton and synchrotron radiation X-ray microspectroscopy

PubMed Central

Ortega, Richard; Devès, Guillaume; Carmona, Asunción

2009-01-01

The direct detection of biologically relevant metals in single cells and of their speciation is a challenging task that requires sophisticated analytical developments. The aim of this article is to present the recent achievements in the field of cellular chemical element imaging, and direct speciation analysis, using proton and synchrotron radiation X-ray micro- and nano-analysis. The recent improvements in focusing optics for MeV-accelerated particles and keV X-rays allow application to chemical element analysis in subcellular compartments. The imaging and quantification of trace elements in single cells can be obtained using particle-induced X-ray emission (PIXE). The combination of PIXE with backscattering spectrometry and scanning transmission ion microscopy provides a high accuracy in elemental quantification of cellular organelles. On the other hand, synchrotron radiation X-ray fluorescence provides chemical element imaging with less than 100 nm spatial resolution. Moreover, synchrotron radiation offers the unique capability of spatially resolved chemical speciation using micro-X-ray absorption spectroscopy. The potential of these methods in biomedical investigations will be illustrated with examples of application in the fields of cellular toxicology, and pharmacology, bio-metals and metal-based nano-particles. PMID:19605403

Method optimization and quality assurance in speciation analysis using high performance liquid chromatography with detection by inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Larsen, Erik H.

1998-02-01

Achievement of optimum selectivity, sensitivity and robustness in speciation analysis using high performance liquid chromatography (HPLC) with inductively coupled mass spectrometry (ICP-MS) detection requires that each instrumental component is selected and optimized with a view to the ideal operating characteristics of the entire hyphenated system. An isocratic HPLC system, which employs an aqueous mobile phase with organic buffer constituents, is well suited for introduction into the ICP-MS because of the stability of the detector response and high degree of analyte sensitivity attained. Anion and cation exchange HPLC systems, which meet these requirements, were used for the seperation of selenium and arsenic species in crude extracts of biological samples. Furthermore, the signal-to-noise ratios obtained for these incompletely ionized elements in the argon ICP were further enhanced by a factor of four by continously introducing carbon as methanol via the mobile phase into the ICP. Sources of error in the HPLC system (column overload), in the sample introduction system (memory by organic solvents) and in the ICP-MS (spectroscopic interferences) and their prevention are also discussed. The optimized anion and cation exchange HPLC-ICP-MS systems were used for arsenic speciation in contaminated ground water and in an in-house shrimp reference sample. For the purpose of verification, HPLC coupled with tandem mass spectrometry with electrospray ionization was additionally used for arsenic speciation in the shrimp sample. With this analytical technique the HPLC retention time in combination with mass analysis of the molecular ions and their collision-induced fragments provide almost conclusive evidence of the identity of the analyte species. The speciation methods are validated by establishing a mass balance of the analytes in each fraction of the extraction procedure, by recovery of spikes and by employing and comparing independent techniques. The urgent need for reference materials certified for elemental species is stressed.

Arsenic Speciation in Groundwater: Role of Thioanions

EPA Science Inventory

The behavior of arsenic in groundwater environments is fundamentally linked to its speciation. Understanding arsenic speciation is important because chemical speciation impacts reactivity, bioavailability, toxicity, and transport and fate processes. In aerobic environments arsen...

Dynamic coupled metal transport-speciation model: application to assess a zinc-contaminated lake.

PubMed

Bhavsar, Satyendra P; Diamond, Miriam L; Gandhi, Nilima; Nilsen, Joel

2004-10-01

A coupled metal transport and speciation/complexation model (TRANSPEC) has been developed to estimate the speciation and fate of multiple interconverting species in surface aquatic systems. Dynamic-TRANSPEC loosely, sequentially couples the speciation/complexation and fate modules that, for the unsteady state formulation, run alternatively at every time step. The speciation module first estimates species abundance using, in this version, MINEQL+ considering time-dependent changes in water and pore-water chemistry. The fate module is based on the quantitative water air sediment interaction (QWASI) model and fugacity/aquivalence formulation, with the option of using a pseudo-steady state solution to account for past discharges. Similarly to the QWASI model for organic contaminants, TRANSPEC assumes the instantaneous equilibrium distribution of metal species among dissolved, colloidal, and particulate phases based on ambient chemistry parameters that can be collected through conventional field methods. The model is illustrated with its application to Ross Lake (Manitoba, Canada) that has elevated Zn concentrations due to discharges over 70 years from a mining operation. Using measurements from field studies, the model reproduces year-round variations in Zn water concentrations. A 10-year projection for current conditions suggests decreasing Zn remobilization and export from the lake. Decreasing Zn loadings increases sediment-to-water transport but decreases water concentrations, and vice versa. Species distribution is affected by pH such that a decrease in pH increases metal export from the lake and vice versa.

From gene trees to a dated allopolyploid network: insights from the angiosperm genus Viola (Violaceae).

PubMed

Marcussen, Thomas; Heier, Lise; Brysting, Anne K; Oxelman, Bengt; Jakobsen, Kjetill S

2015-01-01

Allopolyploidization accounts for a significant fraction of speciation events in many eukaryotic lineages. However, existing phylogenetic and dating methods require tree-like topologies and are unable to handle the network-like phylogenetic relationships of lineages containing allopolyploids. No explicit framework has so far been established for evaluating competing network topologies, and few attempts have been made to date phylogenetic networks. We used a four-step approach to generate a dated polyploid species network for the cosmopolitan angiosperm genus Viola L. (Violaceae Batch.). The genus contains ca 600 species and both recent (neo-) and more ancient (meso-) polyploid lineages distributed over 16 sections. First, we obtained DNA sequences of three low-copy nuclear genes and one chloroplast region, from 42 species representing all 16 sections. Second, we obtained fossil-calibrated chronograms for each nuclear gene marker. Third, we determined the most parsimonious multilabeled genome tree and its corresponding network, resolved at the section (not the species) level. Reconstructing the "correct" network for a set of polyploids depends on recovering all homoeologs, i.e., all subgenomes, in these polyploids. Assuming the presence of Viola subgenome lineages that were not detected by the nuclear gene phylogenies ("ghost subgenome lineages") significantly reduced the number of inferred polyploidization events. We identified the most parsimonious network topology from a set of five competing scenarios differing in the interpretation of homoeolog extinctions and lineage sorting, based on (i) fewest possible ghost subgenome lineages, (ii) fewest possible polyploidization events, and (iii) least possible deviation from expected ploidy as inferred from available chromosome counts of the involved polyploid taxa. Finally, we estimated the homoploid and polyploid speciation times of the most parsimonious network. Homoploid speciation times were estimated by coalescent analysis of gene tree node ages. Polyploid speciation times were estimated by comparing branch lengths and speciation rates of lineages with and without ploidy shifts. Our analyses recognize Viola as an old genus (crown age 31 Ma) whose evolutionary history has been profoundly affected by allopolyploidy. Between 16 and 21 allopolyploidizations are necessary to explain the diversification of the 16 major lineages (sections) of Viola, suggesting that allopolyploidy has accounted for a high percentage-between 67% and 88%-of the speciation events at this level. The theoretical and methodological approaches presented here for (i) constructing networks and (ii) dating speciation events within a network, have general applicability for phylogenetic studies of groups where allopolyploidization has occurred. They make explicit use of a hitherto underexplored source of ploidy information from chromosome counts to help resolve phylogenetic cases where incomplete sequence data hampers network inference. Importantly, the coalescent-based method used herein circumvents the assumption of tree-like evolution required by most techniques for dating speciation events. © The Author(s) 2014. Published by Oxford University Press, on behalf of the Society of Systematic Biologists.

Bats (Chiroptera: Noctilionoidea) Challenge a Recent Origin of Extant Neotropical Diversity.

PubMed

Rojas, Danny; Warsi, Omar M; Dávalos, Liliana M

2016-05-01

The mechanisms underlying the high extant biodiversity in the Neotropics have been controversial since the 19th century. Support for the influence of period-specific changes on diversification often rests on detecting more speciation events during a particular period. The timing of speciation events may reflect the influence of incomplete taxon sampling, protracted speciation, and null processes of lineage accumulation. Here we assess the influence of these factors on the timing of speciation with new multilocus data for New World noctilionoid bats (Chiroptera: Noctilionoidea). Biogeographic analyses revealed the importance of the Neotropics in noctilionoid diversification, and the critical role of dispersal. We detected no shift in speciation rate associated with the Quaternary or pre-Quaternary periods, and instead found an increase in speciation linked to the evolution of the subfamily Stenodermatinae (∼18 Ma). Simulations modeling constant speciation and extinction rates for the phylogeny systematically showed more speciation events in the Quaternary. Since recording more divergence events in the Quaternary can result from lineage accumulation, the age of extant sister species cannot be interpreted as supporting higher speciation rates during this period. Instead, analyzing the factors that influence speciation requires modeling lineage-specific traits and environmental, spatial, and ecological drivers of speciation. © The Author(s) 2016. Published by Oxford University Press, on behalf of the Society of Systematic Biologists. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Frequency-dependent selection predicts patterns of radiations and biodiversity.

PubMed

Melián, Carlos J; Alonso, David; Vázquez, Diego P; Regetz, James; Allesina, Stefano

2010-08-26

Most empirical studies support a decline in speciation rates through time, although evidence for constant speciation rates also exists. Declining rates have been explained by invoking pre-existing niches, whereas constant rates have been attributed to non-adaptive processes such as sexual selection and mutation. Trends in speciation rate and the processes underlying it remain unclear, representing a critical information gap in understanding patterns of global diversity. Here we show that the temporal trend in the speciation rate can also be explained by frequency-dependent selection. We construct a frequency-dependent and DNA sequence-based model of speciation. We compare our model to empirical diversity patterns observed for cichlid fish and Darwin's finches, two classic systems for which speciation rates and richness data exist. Negative frequency-dependent selection predicts well both the declining speciation rate found in cichlid fish and explains their species richness. For groups like the Darwin's finches, in which speciation rates are constant and diversity is lower, speciation rate is better explained by a model without frequency-dependent selection. Our analysis shows that differences in diversity may be driven by incipient species abundance with frequency-dependent selection. Our results demonstrate that genetic-distance-based speciation and frequency-dependent selection are sufficient to explain the high diversity observed in natural systems and, importantly, predict decay through time in speciation rate in the absence of pre-existing niches.

Magnetic fields end-face effect investigation of HTS bulk over PMG with 3D-modeling numerical method

NASA Astrophysics Data System (ADS)

Qin, Yujie; Lu, Yiyun

2015-09-01

In this paper, the magnetic fields end-face effect of high temperature superconducting (HTS) bulk over a permanent magnetic guideway (PMG) is researched with 3D-modeling numerical method. The electromagnetic behavior of the bulk is simulated using finite element method (FEM). The framework is formulated by the magnetic field vector method (H-method). A superconducting levitation system composed of one rectangular HTS bulk and one infinite long PMG is successfully investigated using the proposed method. The simulation results show that for finite geometrical HTS bulk, even the applied magnetic field is only distributed in x-y plane, the magnetic field component Hz which is along the z-axis can be observed interior the HTS bulk.

Relative Bioavailability and Bioaccessability and Speciation of ...

EPA Pesticide Factsheets

Background: Assessment of soil arsenic (As) bioavailability may profoundly affect the extent of remediation required at contaminated sites by improving human exposure estimates. Because small adjustments in soil As bioavailability estimates can significantly alter risk assessments and remediation goals, convenient, rapid, reliable, and inexpensive tools are needed to determine soil As bioavailability. Objectives: We evaluated inexpensive methods for assessing As bioavailability in soil as a means to improve human exposure estimates and potentially reduce remediation costs. Methods: Nine soils from residential sites affected by mining or smelting activity and two National Institute of Standards and Technology standard reference materials were evaluated for As bioavailability, bioaccessibility, and speciation. Arsenic bioavailability was determined using an in vivo mouse model, and As bioaccessibility was determined using the Solubility/Bioavailability Research Consortium in vitro assay. Arsenic speciation in soil and selected soil physicochemical properties were also evaluated to determine whether these parameters could be used as predictors of As bio¬availability and bioaccessibility. Results: In the mouse assay, we compared bioavailabilities of As in soils with that for sodium arsenate. Relative bioavailabilities (RBAs) of soil As ranged from 11% to 53% (mean, 33%). In vitro soil As bioaccessibility values were strongly correlated with soil As RBAs (R

Simultaneous Speciation Analysis of Arsenic, Chromium, and Selenium in the Bioaccessible Fraction for Realistic Risk Assessment of Food Safety.

PubMed

Sadiq, Nausheen W; Beauchemin, Diane

2017-12-19

A simple and fast method was developed for risk assessment of As, Cr, and Se in food, which is demonstrated here using three cooked and uncooked rice samples (basmati as well as organic white and brown rice). The bioaccessible fraction was first determined through online leaching of rice minicolumns (maintained at 37 °C) sequentially with artificial saliva, gastric juice, and intestinal juice while continuously monitoring potentially toxic elements (As, Cr, and Se) by inductively coupled plasma mass spectrometry (ICPMS). Then, a new ion chromatography method with online detection by ICPMS was developed for the simultaneous speciation analysis of As, Cr, and Se in the bioaccessible fraction to determine the portion of these elements that was actually toxic. Using gradient elution, four As species [As(III), As(V), monomethylarsonic acid, and dimethylarsinic acid], two Cr species [Cr(III) and Cr(VI)], and two Se species [Se(IV) and Se(VI)] were separated within 12 min. The simultaneous speciation analysis of As, Cr, and Se revealed that the simple act of cooking can convert all of the carcinogenic Cr(VI) to the safer Cr(III).

Liquid chromatography-hydride generation-atomic absorption spectrometry for the speciation of tin in seafoods.

PubMed

Viñas, Pilar; López-García, Ignacio; Merino-Meroño, Beatriz; Campillo, Natalia; Hernández-Cordóba, Manuel

2004-04-01

Liquid chromatography with hydride generation atomic absorption spectrometry as the detection system was applied to the separation and determination of inorganic tin, tributyltin, dibutyltin, monobutyltin, diphenyltin and monophenyltin. A reversed phase C18 column and a methanol/water/acetic acid (70:27:3, v/v/v) mixture containing 0.05%(v/v) triethylamine and 0.1%(w/v) tropolone as the mobile phase (isocratic elution) were used. Extraction of organotins from the samples was carried out using methanol containing 0.05%(w/v) tropolone, a process that was repeated twice. The supernatants were shaken with water and dichloromethane in a separating funnel and the organic phase was collected and evaporated to dryness. When the method was applied to the speciation of tin in fresh and canned mussels, no organotins above the detection limits were identified in any of the samples, inorganic tin being the only species detected. The reliability of the procedure was checked by analyzing the total tin content of the samples by electrothermal atomic absorption spectrometry and by speciation of tin in a certified reference material, mussel tissue (CRM 477). The method can be used for environmental monitoring of organotins contaminated samples.

Specific extraction of chromium as tetrabutylammonium-chromate and spectrophotometric determination by diphenylcarbazide: speciation of chromium in effluent streams.

PubMed

Noroozifar, M; Khorasani-Motlagh, M

2003-05-01

A very specific, selective, simple, and inexpensive procedure was developed for the speciation of CrVI and CrIII. This method is based on the quantitative extraction of chromate and CrIII (previously oxidized to CrVI) as a tetrabutylammonium-chromate ion-pair in methyl isobutyl ketone (MIBK), and then back extraction and preconcentration with an acidic diphenylcarbazide (DPC) solution. Back extraction was applied to achieve further preconcentration by a final factor of 20. The CrVI-DPC complex was determined in back-extract by a spectrophotometer at 548 nm. Under these extraction conditions, most of the probable concomitant cations and anions remained in the first inorganic phase. The calibration curve was linear up to 0.14 microg L(-1) of CrVI with a detection limit of 2.22 ng L(-1). The developed procedure was found to be suitable for the determination of the CrVI and CrIII species in various natural water samples with a relative standard deviation of better than 1.6%. The method was successfully applied to the speciation of chromium in spiked natural water samples, and also samples of effluent from a leather treatment plant.

Potential application of SERS for arsenic speciation in biological matrices.

PubMed

Yang, Mingwei; Matulis, Shannon; Boise, Lawrence H; McGoron, Anthony J; Cai, Yong

2017-08-01

Speciation of arsenic is usually carried out using chromatography-based methods coupled with spectroscopic determination; however, the inevitable procedures involving sample preparation and separation could potentially alter the integrity of the arsenic metabolites present in biological samples. Surface-enhanced Raman spectroscopy (SERS) could be a promising alternative for providing a reliable arsenic analysis under the influence of a cellular matrix. A method for arsenic speciation using SERS in cellular matrix was developed in this study and four arsenicals were selected, including arsenite (As III ), arsenate (As V ), monomethylarsonic acid (MMA V ) and dimethylarsinic acid (DMA V ). Silver nanoparticles in the form of colliodal suspension with different surface charges, i.e., coated with citrate (AgNPs-Citrate) and spermine (AgNPs-Spermine) were employed as SERS substrates. Adsorption of arsenicals on nanoparticles in colloidal suspensions and the cellular matrix and the pH, size, and zeta potential of the colloidal suspensions were investigated for a better understanding of the SERS signal response of arsenicals in the colloidal suspensions or under the influence of cellular matrix. Arsenicals showed substantially different SERS responses in the two colloidal suspensions, mainly because of the distinct difference in the interaction between the arsenicals and the nanoparticles. Arsenic speciation in cell lysate could be successfully carried out in AgNPs-Spermine suspension, while AgNPs-Citrate could not yield significant SERS signals under the experimental conditions. This study proved that AgNPs-Spermine colloidal suspension could be a promising SERS substrate for studying arsenic metabolism in a biological matrix, reducing the bias caused by traditional techniques that involve sample extraction and pretreatment.

Bulk and molecular-level characterization of laboratory-aged biomass burning organic aerosol from oak leaf and heartwood fuels

NASA Astrophysics Data System (ADS)

Fortenberry, Claire F.; Walker, Michael J.; Zhang, Yaping; Mitroo, Dhruv; Brune, William H.; Williams, Brent J.

2018-02-01

The chemical complexity of biomass burning organic aerosol (BBOA) greatly increases with photochemical aging in the atmosphere, necessitating controlled laboratory studies to inform field observations. In these experiments, BBOA from American white oak (Quercus alba) leaf and heartwood samples was generated in a custom-built emissions and combustion chamber and photochemically aged in a potential aerosol mass (PAM) flow reactor. A thermal desorption aerosol gas chromatograph (TAG) was used in parallel with a high-resolution time-of-flight aerosol mass spectrometer (AMS) to analyze BBOA chemical composition at different levels of photochemical aging. Individual compounds were identified and integrated to obtain relative decay rates for key molecules. A recently developed chromatogram binning positive matrix factorization (PMF) technique was used to obtain mass spectral profiles for factors in TAG BBOA chromatograms, improving analysis efficiency and providing a more complete determination of unresolved complex mixture (UCM) components. Additionally, the recently characterized TAG decomposition window was used to track molecular fragments created by the decomposition of thermally labile BBOA during sample desorption. We demonstrate that although most primary (freshly emitted) BBOA compounds deplete with photochemical aging, certain components eluting within the TAG thermal decomposition window are instead enhanced. Specifically, the increasing trend in the decomposition m/z 44 signal (CO2+) indicates formation of secondary organic aerosol (SOA) in the PAM reactor. Sources of m/z 60 (C2H4O2+), typically attributed to freshly emitted BBOA in AMS field measurements, were also investigated. From the TAG chemical speciation and decomposition window data, we observed a decrease in m/z 60 with photochemical aging due to the decay of anhydrosugars (including levoglucosan) and other compounds, as well as an increase in m/z 60 due to the formation of thermally labile organic acids within the PAM reactor, which decompose during TAG sample desorption. When aging both types of BBOA (leaf and heartwood), the AMS data exhibit a combination of these two contributing effects, causing limited change to the overall m/z 60 signal. Our observations demonstrate the importance of chemically speciated data in fully understanding bulk aerosol measurements provided by the AMS in both laboratory and field studies.

EPAs SPECIATE 4.4 Database: Development and Uses

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency’s (EPA) repository of source category-specific particulate matter (PM), volatile organic gas, and other gas speciation profiles of air pollutant emissions. Abt Associates, Inc. developed SPECIATE 4.4 through a collaborat...

SPECIATE Version 4.4 Database Development Documentation

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency’s (EPA) repository of volatile organic gas and particulate matter (PM) speciation profiles of air pollution sources. Some of the many uses of these source profiles include: (1) creating speciated emissions inventories for regi...

SPECIATE - EPA'S DATABASE OF SPECIATED EMISSION PROFILES

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency's (EPA) repository of total organic compound (TOC) and particulate matter (PM) speciation profiles for emissions from air pollution sources. The data base has recently been updated and an associated report has recently been re...

Speciation has a spatial scale that depends on levels of gene flow.

PubMed

Kisel, Yael; Barraclough, Timothy G

2010-03-01

Area is generally assumed to affect speciation rates, but work on the spatial context of speciation has focused mostly on patterns of range overlap between emerging species rather than on questions of geographical scale. A variety of geographical theories of speciation predict that the probability of speciation occurring within a given region should (1) increase with the size of the region and (2) increase as the spatial extent of intraspecific gene flow becomes smaller. Using a survey of speciation events on isolated oceanic islands for a broad range of taxa, we find evidence for both predictions. The probability of in situ speciation scales with island area in bats, carnivorous mammals, birds, flowering plants, lizards, butterflies and moths, and snails. Ferns are an exception to these findings, but they exhibit high frequencies of polyploid and hybrid speciation, which are expected to be scale independent. Furthermore, the minimum island size for speciation correlates across groups with the strength of intraspecific gene flow, as is estimated from a meta-analysis of published population genetic studies. These results indicate a general geographical model of speciation rates that are dependent on both area and gene flow. The spatial scale of population divergence is an important but neglected determinant of broad-scale diversity patterns.

A new turn-on fluorimetric method for the rapid speciation of Cr(III)/Cr(VI) species in tea samples with rhodamine-based fluorescent reagent

NASA Astrophysics Data System (ADS)

Özyol, Esra; Saçmacı, Şerife; Saçmacı, Mustafa; Ülgen, Ahmet

2018-02-01

A new fluorimetric method with rhodamine-based fluorescent agent was developed for the rapid speciation of Cr(III)/Cr(VI) in tea, soil and water samples. The system, which utilizes a fluorescent reagent, was used for the first time after synthesis/characterization of 3‧,6‧-bis(diethylamino)-2-{[(1E)-(2,4-dimethoxyphenyl)methylene] amino}spiro[isoindole-1,9‧-xanthen]-3(2H)-one (BDAS). The reagent responds instantaneously at room temperature in a 1:1 stoichiometric manner to the amount of Cr(III). The selectivity of this system for Cr(III) over other metal ions is remarkably high, and its sensitivity is below 0.01 mg L- 1 in aqueous solutions which enables a simplification without any pretreatment of the real sample. The method has a wide linear range of 0.1-10 mg L- 1 and a detection limit of 0.15 μg L- 1 for Cr(III) while the relative standard deviation was 0.1% for 0.1 mg L- 1 Cr(III) concentration. The results of detection and recovery experiments for Cr(III) in tea, soil and water were satisfactory, indicating that the method has better feasibility and application potential in the routine determination and speciation of Cr(III)/Cr(VI). The results of analysis of the certified reference material (INCT-TL-1 tea sample and CWW-TM-D waste water) are in good agreement with the certified value.

SPECIATE--EPA'S DATABASE OF SPECIATED EMISSION PROFILES

EPA Science Inventory

SPECIATE is EPA's repository of Total Organic Compound and Particulate Matter speciated profiles for a wide variety of sources. The profiles in this system are provided for air quality dispersion modeling and as a library for source-receptor and source apportionment type models. ...

SPECIATE 4.4: The Bridge Between Emissions Characterization and Modeling

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency’s (EPA) repository of volatile organic gas and particulate matter (PM) speciation profiles of air pollution sources. Some of the many uses of these source profiles include: (1) creating speciated emissions inventories for...

The importance of trace element speciation in biomedical science.

PubMed

Templeton, Douglas M

2003-04-01

According to IUPAC terminology, trace element speciation reflects differences in chemical composition at multiple levels from nuclear and electronic structure to macromolecular complexation. In the medical sciences, all levels of composition are important in various circumstances, and each can affect the bioavailability, distribution, physiological function, toxicity, diagnostic utility, and therapeutic potential of an element. Here we discuss, with specific examples, three biological principles in the intimate relation between speciation and biological behavior: i) the kinetics of interconversion of species determines distribution within the organism, ii) speciation governs transport across various biological barriers, and iii) speciation can limit potentially undesirable interactions between physiologically essential elements. We will also describe differences in the speciation of iron in states of iron overload, to illustrate how speciation analysis can provide insight into cellular processes in human disease.

Examination of Arsenic Speciation in Sulfidic Solutions Using X-ray Absorption Spectroscopy

EPA Science Inventory

The chemical speciation of arsenic in sulfidic waters is complicated by the existence of thioarsenic species. The purpose of this research was to use advanced spectroscopy techniques along with speciation modeling and chromatography to elucidate the chemical speciation of As in ...

MODELING MONOMETHYLMERCURY AND TRIBUTYLTIN SPECIATION WITH EPA'S GEOCHEMICAL SPECIATION MODEL MINTEQA2

EPA Science Inventory

Given the complexity of the various, simultaneous (and competing) equilibrium reactions governing the speciation of ionic species in aquatic systems, EPA has developed and distributed the geochemical speciation model MINTEQA2 (Brown and Allison, 1987, Allison et al., 1991; Hydrog...

Speciation genetics: current status and evolving approaches

PubMed Central

Wolf, Jochen B. W.; Lindell, Johan; Backström, Niclas

2010-01-01

The view of species as entities subjected to natural selection and amenable to change put forth by Charles Darwin and Alfred Wallace laid the conceptual foundation for understanding speciation. Initially marred by a rudimental understanding of hereditary principles, evolutionists gained appreciation of the mechanistic underpinnings of speciation following the merger of Mendelian genetic principles with Darwinian evolution. Only recently have we entered an era where deciphering the molecular basis of speciation is within reach. Much focus has been devoted to the genetic basis of intrinsic postzygotic isolation in model organisms and several hybrid incompatibility genes have been successfully identified. However, concomitant with the recent technological advancements in genome analysis and a newfound interest in the role of ecology in the differentiation process, speciation genetic research is becoming increasingly open to non-model organisms. This development will expand speciation research beyond the traditional boundaries and unveil the genetic basis of speciation from manifold perspectives and at various stages of the splitting process. This review aims at providing an extensive overview of speciation genetics. Starting from key historical developments and core concepts of speciation genetics, we focus much of our attention on evolving approaches and introduce promising methodological approaches for future research venues. PMID:20439277

Application of Atmospheric Pressure Photoionization H/D-exchange Mass Spectrometry for Speciation of Sulfur-containing Compounds.

PubMed

Acter, Thamina; Kim, Donghwi; Ahmed, Arif; Ha, Ji-Hyoung; Kim, Sunghwan

2017-08-01

Herein we report the observation of atmospheric pressure in-source hydrogen-deuterium exchange (HDX) of thiol group for the first time. The HDX for thiol group was optimized for positive atmospheric pressure photoionization (APPI) mass spectrometry (MS). The optimized HDX-MS was applied for 31 model compounds (thiols, thiophenes, and sulfides) to demonstrate that exchanged peaks were observed only for thiols. The optimized method has been successfully applied to the isolated fractions of sulfur-rich oil samples. The exchange of one and two thiol hydrogens with deuterium was observed in the thiol fraction; no HDX was observed in the other fractions. Thus, the results presented in this study demonstrate that the HDX-MS method using APPI ionization source can be effective for speciation of sulfur compounds. This method has the potential to be used to access corrosion problems caused by thiol-containing compounds. Graphical Abstract ᅟ.

METHODS FOR THE SPECIATION OF METALS IN SOILS: A REVIEW

EPA Science Inventory

The inability to determine metal species in soils hampers efforts to understand the mobility, bioavailability, and fate of contaminant metals in environmental systems, to assess health risks posed by them, and to develop methods to remediate metal contaminated sites. Fortunately,...

METAL SPECIATION IN SOIL, SEDIMENT, AND WATER SYSTEMS VIA SYNCHROTRON RADIATION RESEARCH

EPA Science Inventory

Metal contaminated environmental systems (soils, sediments, and water) have challenged researchers for many years. Traditional methods of analysis have employed extraction methods to determine total metal content and define risk based on the premise that as metal concentration in...

Assessment of Important SPECIATE Profiles in EPA’s Emissions Modeling Platform and Current Data Gaps

EPA Science Inventory

The US Environmental Protection Agency (EPA)’s SPECIATE database contains speciation profiles for both particulate matter (PM) and volatile organic compounds (VOCs) that are key inputs for creating speciated emission inventories for air quality modeling. The objective of th...

Extraordinarily rapid speciation in a marine fish

PubMed Central

Momigliano, Paolo; Jokinen, Henri; Fraimout, Antoine; Florin, Ann-Britt; Norkko, Alf; Merilä, Juha

2017-01-01

Divergent selection may initiate ecological speciation extremely rapidly. How often and at what pace ecological speciation proceeds to yield strong reproductive isolation is more uncertain. Here, we document a case of extraordinarily rapid speciation associated with ecological selection in the postglacial Baltic Sea. European flounders (Platichthys flesus) in the Baltic exhibit two contrasting reproductive behaviors: pelagic and demersal spawning. Demersal spawning enables flounders to thrive in the low salinity of the Northern Baltic, where eggs cannot achieve neutral buoyancy. We show that demersal and pelagic flounders are a species pair arising from a recent event of speciation. Despite having a parapatric distribution with extensive overlap, the two species are reciprocally monophyletic and show strongly bimodal genotypic clustering and no evidence of contemporary migration, suggesting strong reproductive isolation. Divergence across the genome is weak but shows strong signatures of selection, a pattern suggestive of a recent ecological speciation event. We propose that spawning behavior in Baltic flounders is the trait under ecologically based selection causing reproductive isolation, directly implicating a process of ecological speciation. We evaluated different possible evolutionary scenarios under the approximate Bayesian computation framework and estimate that the speciation process started in allopatry ∼2,400 generations ago, following the colonization of the Baltic by the demersal lineage. This is faster than most known cases of ecological speciation and represents the most rapid event of speciation ever reported for any marine vertebrate. PMID:28533412

Using SINEs to probe ancient explosive speciation: "hidden" radiation of African cichlids?

PubMed

Terai, Yohey; Takahashi, Kazuhiko; Nishida, Mutsumi; Sato, Tetsu; Okada, Norihiro

2003-06-01

Cichlid fishes of the east African Great Lakes represent a paradigm of adaptive radiation. We conducted a phylogenetic analysis of cichlids including pan-African and west African species by using insertion patterns of short interspersed elements (SINEs) at orthologous loci. The monophyly of the east African cichlids was consistently supported by seven independent insertions of SINE sequences that are uniquely shared by these species. In addition, data from four other loci indicated that the genera Tilapia (pan-African) and Steatocranus (west African) are the closest relatives to east African cichlids. However, relationships among Tilapia, Steatocranus, and the east African clade were ambiguous because of incongruencies among topologies suggested by insertion patterns of SINEs at six other loci. One plausible explanation for this phenomenon is incomplete lineage sorting of alleles containing or missing a SINE insertion at these loci during ancestral speciation. Such incomplete sorting may have taken place earlier than 14 MYA, followed by random and stochastic fixation of the alleles in subsequent lineages. These observations prompted us to consider the possibility that cichlid speciation occurred at an accelerated rate during this period when the African Great Lakes did not exist. The SINE method could be useful for detecting ancient exclusive speciation events that tend to remain hidden during conventional sequence analyses because of accumulated point mutations.

Moving Speciation Genetics Forward: Modern Techniques Build on Foundational Studies in Drosophila.

PubMed

Castillo, Dean M; Barbash, Daniel A

2017-11-01

The question of how new species evolve has been examined at every level, from macroevolutionary patterns of diversification to molecular population genetic analyses of specific genomic regions between species pairs. Drosophila has been at the center of many of these research efforts. Though our understanding of the speciation process has grown considerably over the past few decades, very few genes have been identified that contribute to barriers to reproduction. The development of advanced molecular genetic and genomic methods provides promising avenues for the rapid discovery of more genes that contribute to speciation, particularly those involving prezygotic isolation. The continued expansion of tools and resources, especially for species other than Drosophila melanogaster , will be most effective when coupled with comparative approaches that reveal the genetic basis of reproductive isolation across a range of divergence times. Future research programs in Drosophila have high potential to answer long-standing questions in speciation. These include identifying the selective forces that contribute to divergence between populations and the genetic basis of traits that cause reproductive isolation. The latter can be expanded upon to understand how the genetic basis of reproductive isolation changes over time and whether certain pathways and genes are more commonly involved. Copyright © 2017 by the Genetics Society of America.

Speciation and bioavailability of some heavy metals in agricultural soils used for cultivating various vegetables in Bedugul, Bali

NASA Astrophysics Data System (ADS)

Siaka, I. Made; Utama, I. Made Supartha; Manuaba, I. B. Putra; Adnyana, I. Made; Sahara, Emmy

2016-03-01

This paper discusses the speciation and bioavailability of some heavy metals in agricultural soils used to cultivate various vegetables in Bedugul, Bali. Vegetables grown on contaminated soils where agrochemicals were applied uncontrolled could contain a number of heavy metals. This could occur in the vegetables produced from agricultural soils of Bedugul as the farmers applied agrochemicals excessively. In considering the metals transport to the vegetables, a speciation and bioavailability methods were necessary to be studied. Wet digestion and sequential extraction techniques were employed to the sample prior to the metals measurement by AAS. The results showed that the average concentrations of Pb, Cu, Cd, Cr, and Zn in the soils were 38.531, 132.126, 7.689, 15.952, and 147.275 mg/kg, respectively. The highest concentrations of Pb and Zn were found in the soil for cultivating lettuce, Cd and Cr in the soil for tomato, and Cu in the soil for potatoes. It was found that the speciation of Pb, Cu, Cd, and Cr were predominantly bound to Fe-Mn oxides fraction, while Zn was mostly associated with the EFLE (easily, freely, leachable, and exchangeable) fractions. The highest bioavailability among the metals in the studied soils was Cr, while the lowest was Cu.

Speciation of inorganic selenium and selenoamino acids by an HPLC-UV-HG-AFS system.

PubMed

Ipolyi, I; Corns, W; Stockwell, P; Fodor, P

2001-01-01

For the on-line speciation of selenocystine (SeCys), selenomethionine (SeMet), selenoethionine (SeEt), selenite (Se(IV)) and selenate (Se(VI)), a high-performance liquid chromatography-UV irradiation-hydride generation-atomic fluorescence spectro- metric method is described. Separation was carried out on a conventional reversed-phase C18 column modified with didodecyl- dimethylammonium bromide with gradient elution applying two concentrations of ammonium acetate as the mobile phase. UV irradiation and hydride generation parameters were optimized. The obtained detection limits for SeCys, SeMet, SeEt, Se(IV) and Se(VI) were 0.31, 0.43, 0.7, 0.44 and 0.32 ng ml(-1), respectively, using a 100-microl loop. The method was tested with spiked mineral water and two volunteers' urine samples.

Speciation of inorganic selenium and selenoamino acids by an HPLC-UV-HG-AFS system

PubMed Central

Ipolyi, I.; Corns, W.; Stockwell, P.; Fodor, P.

2001-01-01

For the on-line speciation of selenocystine (SeCys), selenomethionine (SeMet), selenoethionine (SeEt), selenite (Se(IV)) and selenate (Se(VI)), a high-performance liquid chromatography-UV irradiation-hydride generation-atomic fluorescence spectro- metric method is described. Separation was carried out on a conventional reversed-phase C18 column modified with didodecyl- dimethylammonium bromide with gradient elution applying two concentrations of ammonium acetate as the mobile phase. UV irradiation and hydride generation parameters were optimized. The obtained detection limits for SeCys, SeMet, SeEt, Se(IV) and Se(VI) were 0.31, 0.43, 0.7, 0.44 and 0.32 ng ml−1, respectively, using a 100-wl loop. The method was tested with spiked mineral water and two volunteers' urine samples. PMID:18924707

Evolutionary Roots and Diversification of the Genus Aeromonas.

PubMed

Sanglas, Ariadna; Albarral, Vicenta; Farfán, Maribel; Lorén, J G; Fusté, M C

2017-01-01

Despite the importance of diversification rates in the study of prokaryote evolution, they have not been quantitatively assessed for the majority of microorganism taxa. The investigation of evolutionary patterns in prokaryotes constitutes a challenge due to a very scarce fossil record, limited morphological differentiation and frequently complex taxonomic relationships, which make even species recognition difficult. Although the speciation models and speciation rates in eukaryotes have traditionally been established by analyzing the fossil record data, this is frequently incomplete, and not always available. More recently, several methods based on molecular sequence data have been developed to estimate speciation and extinction rates from phylogenies reconstructed from contemporary taxa. In this work, we determined the divergence time and temporal diversification of the genus Aeromonas by applying these methods widely used with eukaryotic taxa. Our analysis involved 150 Aeromonas strains using the concatenated sequences of two housekeeping genes (approximately 2,000 bp). Dating and diversification model analyses were performed using two different approaches: obtaining the consensus sequence from the concatenated sequences corresponding to all the strains belonging to the same species, or generating the species tree from multiple alignments of each gene. We used BEAST to perform a Bayesian analysis to estimate both the phylogeny and the divergence times. A global molecular clock cannot be assumed for any gene. From the chronograms obtained, we carried out a diversification analysis using several approaches. The results suggest that the genus Aeromonas began to diverge approximately 250 millions of years (Ma) ago. All methods used to determine Aeromonas diversification gave similar results, suggesting that the speciation process in this bacterial genus followed a rate-constant (Yule) diversification model, although there is a small probability that a slight deceleration occurred in recent times. We also determined the constant of diversification (λ) values, which in all cases were very similar, about 0.01 species/Ma, a value clearly lower than those described for different eukaryotes.

Evolutionary Roots and Diversification of the Genus Aeromonas

PubMed Central

Sanglas, Ariadna; Albarral, Vicenta; Farfán, Maribel; Lorén, J. G.; Fusté, M. C.

2017-01-01

Despite the importance of diversification rates in the study of prokaryote evolution, they have not been quantitatively assessed for the majority of microorganism taxa. The investigation of evolutionary patterns in prokaryotes constitutes a challenge due to a very scarce fossil record, limited morphological differentiation and frequently complex taxonomic relationships, which make even species recognition difficult. Although the speciation models and speciation rates in eukaryotes have traditionally been established by analyzing the fossil record data, this is frequently incomplete, and not always available. More recently, several methods based on molecular sequence data have been developed to estimate speciation and extinction rates from phylogenies reconstructed from contemporary taxa. In this work, we determined the divergence time and temporal diversification of the genus Aeromonas by applying these methods widely used with eukaryotic taxa. Our analysis involved 150 Aeromonas strains using the concatenated sequences of two housekeeping genes (approximately 2,000 bp). Dating and diversification model analyses were performed using two different approaches: obtaining the consensus sequence from the concatenated sequences corresponding to all the strains belonging to the same species, or generating the species tree from multiple alignments of each gene. We used BEAST to perform a Bayesian analysis to estimate both the phylogeny and the divergence times. A global molecular clock cannot be assumed for any gene. From the chronograms obtained, we carried out a diversification analysis using several approaches. The results suggest that the genus Aeromonas began to diverge approximately 250 millions of years (Ma) ago. All methods used to determine Aeromonas diversification gave similar results, suggesting that the speciation process in this bacterial genus followed a rate-constant (Yule) diversification model, although there is a small probability that a slight deceleration occurred in recent times. We also determined the constant of diversification (λ) values, which in all cases were very similar, about 0.01 species/Ma, a value clearly lower than those described for different eukaryotes. PMID:28228750

Identification of Martian Regolith Sulfur Components in Shergottites Using Sulfur K Xanes and Fe/S Ratios

NASA Technical Reports Server (NTRS)

Sutton, S. R.; Ross, D. K.; Rao, M. N.; Nyquist, L. E.

2014-01-01

Based on isotopic anomalies in Kr and Sm, Sr-isotopes, S-isotopes, XANES results on S-speciation, Fe/S ratios in sulfide immiscible melts [5], and major element correlations with S determined in impact glasses in EET79001 Lith A & Lith B and Tissint, we have provided very strong evidence for the occurrence of a Martian regolith component in some impact melt glasses in shergottites. Using REE measurements by LA-ICP-MS in shergottite impact glasses, Barrat and co-workers have recently reported conflicting conclusions about the occurrence of Martian regolith components: (a) Positive evidence was reported for a Tissint impact melt, but (b) Negative evidence for impact melt in EET79001 and another impact melt in Tissint. Here, we address some specific issues related to sulfur speciation and their relevance to identifying Martian regolith components in impact glasses in EET79001 and Tissint using sulfur K XANES and Fe/S ratios in sulfide immiscible melts. XANES and FE-SEM measurements in approx. 5 micron size individual sulfur blebs in EET79001 and Tissint glasses are carried out by us using sub-micron size beams, whereas Barrat and coworkers used approx. 90 micron size laser spots for LA- ICP-MS to determine REE abundances in bulk samples of the impact melt glasses. We contend that Martian regolith components in some shergottite impact glasses are present locally, and that studying impact melts in various shergottites can give evidence both for and against regolith components because of sample heterogeneity.

OPTIMIZATION OF RAMAN SPECTROSCOPY FOR SPECIATION OF ORGANICS IN WATER

EPA Science Inventory

We describe herein a method for determining constants for simultaneously occurring, site-specific "microequilibria" (as with tautomers) for organics in water. The method is based in part on modeling temperature-variant Raman spectra according to the van't Hoff equation. Spectra a...

TANK 18-F AND 19-F TANK FILL GROUT SCALE UP TEST SUMMARY

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stefanko, D.; Langton, C.

2012-01-03

High-level waste (HLW) tanks 18-F and 19-F have been isolated from FTF facilities. To complete operational closure the tanks will be filled with grout for the purpose of: (1) physically stabilizing the tanks, (2) limiting/eliminating vertical pathways to residual waste, (3) entombing waste removal equipment, (4) discouraging future intrusion, and (5) providing an alkaline, chemical reducing environment within the closure boundary to control speciation and solubility of select radionuclides. This report documents the results of a four cubic yard bulk fill scale up test on the grout formulation recommended for filling Tanks 18-F and 19-F. Details of the scale upmore » test are provided in a Test Plan. The work was authorized under a Technical Task Request (TTR), HLE-TTR-2011-008, and was performed according to Task Technical and Quality Assurance Plan (TTQAP), SRNL-RP-2011-00587. The bulk fill scale up test described in this report was intended to demonstrate proportioning, mixing, and transportation, of material produced in a full scale ready mix concrete batch plant. In addition, the material produced for the scale up test was characterized with respect to fresh properties, thermal properties, and compressive strength as a function of curing time.« less

Arsenic speciation in sinter mineralization from a hydrothermal channel of El Tatio geothermal field, Chile

NASA Astrophysics Data System (ADS)

Alsina, Marco A.; Zanella, Luciana; Hoel, Cathleen; Pizarro, Gonzalo E.; Gaillard, Jean-François; Pasten, Pablo A.

2014-10-01

El Tatio geothermal field is the principal natural source of arsenic for the Loa River, the main surface water resource in the hyper-arid Atacama Desert (Antofagasta Region, Northern Chile). Prior investigations by bulk X-ray absorption spectroscopy have identified hydrous ferric oxides as the principal arsenic-containing phase in sinter material from El Tatio, suggesting sorption as the main mechanism for arsenic scavenging by the solid phases of these hot spring environments. Here we examine siliceous sinter material sampled from a hydrothermal channel using synchrotron based X-ray micro-probe techniques, including As and Fe Kα X-ray fluorescence (μ-XRF), As K-edge X-ray absorption near edge structure (μ-XANES), and X-ray diffraction (μ-XRD). Least-squares linear fitting of μ-XANES spectra shows that arsenic is predominantly present as arsenate sorbed on hydrous ferric oxides (63% molar proportion), but we also identify nodular arsenide micro-mineralizations (37% molar proportion) similar to loellingite (FeAs2), not previously detected during bulk-scale analysis of the sinter material. Presence of arsenide mineralizations indicates development of anoxic environments on the surface of the siliceous sinter, and suggests a more complex biogeochemistry for arsenic than previously observed for circum-neutral pH brine hot spring environments.

X-ray Microprobe Investigations of Elemental Distributions and Concentrations at Mineral-Microbe Interfaces

NASA Astrophysics Data System (ADS)

Kemner, K. M.; Kelly, S. D.; O'Loughlin, E. J.; Lai, B.; Maser, J.; Cai, Z.; Londer, Y.; Schiffer, M.; Nealson, K.

2003-12-01

Understanding the fate of heavy-metal contaminants in the environment is of fundamental importance in the development and evaluation of effective remediation and sequestration strategies. Bacteria and the extracellular material associated with them are thought to play a key role in determining a contaminant's speciation and thus its mobility in the environment. Additionally, the metabolism and surface properties of bacteria can be quite different depending upon whether the bacteria exhibit a planktonic (free-floating) or biofilm (surface adhered) habit. The microenvironment at and adjacent to actively metabolizing cells also can be significantly different from the bulk environment. Thus, to understand the microscopic physical, geological, chemical, and biological interfaces that determine a contaminant's macroscopic fate, the spatial distribution and chemical speciation of contaminants and elements that are key to biological processes must be characterized at micron and submicron lengthscales for bacteria in both planktonic and adhered states. Hard x-ray microimaging is a powerful technique for the element-specific investigation of complex environmental samples at the needed micron and submicron resolution. An important advantage of these techniques results from the large penetration depth of hard x-rays in water. This advantage minimizes the requirements for sample preparation and allows the detailed study of hydrated samples. The objectives of the studies to be presented are (1) to determine the spatial distribution, concentration, and chemical speciation of metals at, in, and near bacteria and bacteria-geosurface interfaces, (2) to use this information to identify the metabolic processes occurring within the microbes, and (3) to identify the interactions occurring near these interfaces among the metals, mineral surfaces, and bacteria under a variety of conditions. We have used x-ray fluorescence microscopy to investigate the spatial distribution of 3d elements in Pseudomonas fluorescens cells in both planktonic and surface-adhered states. We have used x-ray fluorescence spectromicroscopy to investigate the chemical speciation and distribution of Cr that was introduced to these cells as Cr(VI). Additionally, we have used these techniques to identify the distribution of an over expressed cytochrome c7 in individual E. coli. Finally, we have used x-ray fluorescence microscopy to investigate Shewanella oneidensis MR-1 cells adhered to iron oxyhydroxide thin films. The zone plate used in these microscopy experiments produced a focused beam with a cross section (and hence spatial resolution) of 100-300 nanometers. Results from x-ray fluorescence imaging experiments indicate that the distribution of P, S, Cl, Ca, Fe, Ni, Cu, and Zn can define the location of the microbe. Additionally, quantitative elemental analysis of individual microbes identified significant changes in concentration of 3d transition elements depending on the age of the culture and the type of electron acceptor presented to the microbes. These results and a discussion of the use of this technique for identifying metabolic states of individual microbes within communities and the chemical speciation of metal contaminants at the mineral-microbe interface will be presented.

Assessment of important SPECIATE Profiles in EPA’s Emissions Modeling Platform and Current Data Gaps (US EPA 2017 International Emissions Inventory Conference)

EPA Science Inventory

The US Environmental Protection Agency (EPA)’s SPECIATE database contains speciation profiles for both particulate matter (PM) and volatile organic compounds (VOCs) that are key inputs for creating speciated emission inventories for air quality modeling. The objective of th...

A complex speciation–richness relationship in a simple neutral model

PubMed Central

Desjardins-Proulx, Philippe; Gravel, Dominique

2012-01-01

Speciation is the “elephant in the room” of community ecology. As the ultimate source of biodiversity, its integration in ecology's theoretical corpus is necessary to understand community assembly. Yet, speciation is often completely ignored or stripped of its spatial dimension. Recent approaches based on network theory have allowed ecologists to effectively model complex landscapes. In this study, we use this framework to model allopatric and parapatric speciation in networks of communities. We focus on the relationship between speciation, richness, and the spatial structure of communities. We find a strong opposition between speciation and local richness, with speciation being more common in isolated communities and local richness being higher in more connected communities. Unlike previous models, we also find a transition to a positive relationship between speciation and local richness when dispersal is low and the number of communities is small. We use several measures of centrality to characterize the effect of network structure on diversity. The degree, the simplest measure of centrality, is the best predictor of local richness and speciation, although it loses some of its predictive power as connectivity grows. Our framework shows how a simple neutral model can be combined with network theory to reveal complex relationships between speciation, richness, and the spatial organization of populations. PMID:22957181

Divergence with gene flow across a speciation continuum of Heliconius butterflies.

PubMed

Supple, Megan A; Papa, Riccardo; Hines, Heather M; McMillan, W Owen; Counterman, Brian A

2015-09-24

A key to understanding the origins of species is determining the evolutionary processes that drive the patterns of genomic divergence during speciation. New genomic technologies enable the study of high-resolution genomic patterns of divergence across natural speciation continua, where taxa pairs with different levels of reproductive isolation can be used as proxies for different stages of speciation. Empirical studies of these speciation continua can provide valuable insights into how genomes diverge during speciation. We examine variation across a handful of genomic regions in parapatric and allopatric populations of Heliconius butterflies with varying levels of reproductive isolation. Genome sequences were mapped to 2.2-Mb of the H. erato genome, including 1-Mb across the red color pattern locus and multiple regions unlinked to color pattern variation. Phylogenetic analyses reveal a speciation continuum of pairs of hybridizing races and incipient species in the Heliconius erato clade. Comparisons of hybridizing pairs of divergently colored races and incipient species reveal that genomic divergence increases with ecological and reproductive isolation, not only across the locus responsible for adaptive variation in red wing coloration, but also at genomic regions unlinked to color pattern. We observe high levels of divergence between the incipient species H. erato and H. himera, suggesting that divergence may accumulate early in the speciation process. Comparisons of genomic divergence between the incipient species and allopatric races suggest that limited gene flow cannot account for the observed high levels of divergence between the incipient species. Our results provide a reconstruction of the speciation continuum across the H. erato clade and provide insights into the processes that drive genomic divergence during speciation, establishing the H. erato clade as a powerful framework for the study of speciation.

Erosive processes after tectonic uplift stimulate vicariant and adaptive speciation: evolution in an Afrotemperate-endemic paper daisy genus

PubMed Central

2014-01-01

Background The role of tectonic uplift in stimulating speciation in South Africa’s only alpine zone, the Drakensberg, has not been explicitly examined. Tectonic processes may influence speciation both through the creation of novel habitats and by physically isolating plant populations. We use the Afrotemperate endemic daisy genus Macowania to explore the timing and mode (geographic versus adaptive) of speciation in this region. Between sister species pairs we expect high morphological divergence where speciation has happened in sympatry (adaptive) while with geographic (vicariant) speciation we may expect to find less morphological divergence and a greater degree of allopatry. A dated molecular phylogenetic hypothesis for Macowania elucidates species’ relationships and is used to address the potential impact of uplift on diversification. Morphological divergence of a small sample of reproductive and vegetative characters, used as a proxy for adaptive divergence, is measured against species’ range distributions to estimate mode of speciation across two subclades in the genus. Results The Macowania crown age is consistent with the hypothesis of post-uplift diversification, and we find evidence for both vicariant and adaptive speciation between the two subclades within Macowania. Both subclades exhibit strong signals of range allopatry, suggesting that geographic isolation was important in speciation. One subclade, associated with dry, rocky environments at high altitudes, shows very little morphological and ecological differentiation but high range allopatry. The other subclade occupies a greater variety of habitats and exhibits far greater morphological differentiation, but contains species with overlapping distribution ranges. Conclusions Species in Macowania are likely to have diversified in response to tectonic uplift, and we invoke uplift and uplift-mediated erosion as the main drivers of speciation. The greater relative morphological divergence in sympatric species of Macowania indicates that speciation in the non-sympatric taxa may not have required obvious adaptive differences, implying that simple geographic isolation was the driving force for speciation (‘neutral speciation’). PMID:24524661

[Determination of cadmium by HG-aFS in soil of virescent zone in Chengdu city].

PubMed

Chen, Yuan; Zeng, Ying; Wu, Hong-ji; Wang, Qin-er

2008-12-01

The different speciations of cadmium in soil samples from Chengdu greenbelt were extracted by Tessier sequential extraction method. The contents of total cadmium and different speciation cadmium were determined using HG-AFS. Under optimization condition of HG-AFS and using 2% HCl as medium, and 30 g x L(-1) KBH4 as reductive reagent, 1 mg x L(-1) Co2+ acting together with 10 g x L(-1) CH4N2S can advance the generating efficiency of cadmium compound. The effects of the coexisting elements in soil on the determination of cadmium can be reduced if certain amount of Na4P2O7, K2SO4 and BaCl2 are added. The linear range is 0-10 mg x L(-1) with r=0.9991 and the detection limit is 0.016 mg x L(-1). The recovery is 97.80%-100.2% with RSD of 1.93%. The analytical method is very sensitive and accurate. The distribution of average percentage of five speciations of cadmium in experimental soil samples is: residual fraction (62.1%) > exchangeable fraction (11.7%) > Fe-Mn oxide-bound (9.71%) > carbonate-bound (4.17%) > organic-bound (3.47%). Although residual fraction is the main speciation of cadmium in soil, the content of exchangeable fraction is relatively high. Thus the bioactivity of cadmium in the research area should be recognized. The concentration of cadmium exceeds the country standard in 19 soil sample, accounting for 86. 4% of all soil samples. The soil from Chengdu greenbelt located in 1st ring road, 2nd ring road and 3rd ring road was polluted to different degree. The relative pollution magnitude of them is: 2nd ring road > 1st ring road > 3rd ring road.

Lineage diversification of fringe-toed lizards (Phrynosomatidae: Uma notata complex) in the Colorado Desert: Delimiting species in the presence of gene flow

USGS Publications Warehouse

Gottscho, Andrew D.; Wood, Dustin A.; Vandergast, Amy; Lemos Espinal, Julio A.; Gatesy, John; Reeder, Tod

2017-01-01

Multi-locus nuclear DNA data were used to delimit species of fringe-toed lizards of theUma notata complex, which are specialized for living in wind-blown sand habitats in the deserts of southwestern North America, and to infer whether Quaternary glacial cycles or Tertiary geological events were important in shaping the historical biogeography of this group. We analyzed ten nuclear loci collected using Sanger sequencing and genome-wide sequence and single-nucleotide polymorphism (SNP) data collected using restriction-associated DNA (RAD) sequencing. A combination of species discovery methods (concatenated phylogenies, parametric and non-parametric clustering algorithms) and species validation approaches (coalescent-based species tree/isolation-with-migration models) were used to delimit species, infer phylogenetic relationships, and to estimate effective population sizes, migration rates, and speciation times. Uma notata, U. inornata, U. cowlesi, and an undescribed species from Mohawk Dunes, Arizona (U. sp.) were supported as distinct in the concatenated analyses and by clustering algorithms, and all operational taxonomic units were decisively supported as distinct species by ranking hierarchical nested speciation models with Bayes factors based on coalescent-based species tree methods. However, significant unidirectional gene flow (2NM >1) from U. cowlesi and U. notata into U. rufopunctata was detected under the isolation-with-migration model. Therefore, we conservatively delimit four species-level lineages within this complex (U. inornata, U. notata, U. cowlesi, and U. sp.), treating U. rufopunctata as a hybrid population (U. notata x cowlesi). Both concatenated and coalescent-based estimates of speciation times support the hypotheses that speciation within the complex occurred during the late Pleistocene, and that the geological evolution of the Colorado River delta during this period was an important process shaping the observed phylogeographic patterns.

Cellular processing of gold nanoparticles: CE-ICP-MS evidence for the speciation changes in human cytosol.

PubMed

Legat, Joanna; Matczuk, Magdalena; Timerbaev, Andrei R; Jarosz, Maciej

2018-01-01

The cellular uptake of gold nanoparticles (AuNPs) may (or may not) affect their speciation, but information on the chemical forms in which the particles exist in the cell remains obscure. An analytical method based on the use of capillary electrophoresis hyphenated with inductively coupled plasma mass spectrometry (ICP-MS) has been proposed to shed light on the intracellular processing of AuNPs. It was observed that when being introduced into normal cytosol, the conjugates of 10-50 nm AuNPs with albumin evolved in human serum stayed intact. On the contrary, under simulated cancer cytosol conditions, the nanoconjugates underwent decomposition, the rate of which and the resulting metal speciation patterns were strongly influenced by particle size. The new peaks that appeared in ICP-MS electropherograms could be ascribed to nanosized species, as upon ultracentrifugation, they quantitatively precipitated whereas the supernatant showed only trace Au signals. Our present study is the first step to unravel a mystery of the cellular chemistry for metal-based nanomedicines.

Development of a FI-HG-ICP-OES solid phase preconcentration system for inorganic selenium speciation in Argentinean beverages.

PubMed

Escudero, Luis A; Pacheco, Pablo H; Gasquez, José A; Salonia, José A

2015-02-15

A preconcentration system has been developed to determine inorganic selenium species. Selenium was retained by a column filled with polyvinyl chloride (PVC) with lanthanum hydroxide co-precipitation. Speciation was achieved by selective photoreduction previous Se preconcentration. The retention pH was optimized at 10.0. Two multivariate calibrations and a central composite design were employed for optimization of the system. Sample, reagents and acid flow rates are significant variables affecting the system. Employing HG-ICP-OES as detection, the optimized system reached a detection limit of 0.03μg/L, and an enhancement factor of 14875 (25 for preconcentration system, 595 for hydride generation). To verify the method' accuracy, two certified reference materials, BCR® 414 Plankton & IRMM-804 Rice Flour, were analysed. The system was applied to inorganic selenium speciation in several Argentinean beverages to estimate their selenium contribution to diet. Copyright © 2014 Elsevier Ltd. All rights reserved.

Inductively coupled plasma mass spectrometry and electrospray mass spectrometry for speciation analysis: applications and instrumentation

NASA Astrophysics Data System (ADS)

Rosen, Amy L.; Hieftje, Gary M.

2004-02-01

To gain an understanding of the function, toxicity and distribution of trace elements, it is necessary to determine not only the presence and concentration of the elements of interest, but also their speciation, by identifying and characterizing the compounds within which each is present. For sensitive detection of compounds containing elements of interest, inductively coupled plasma mass spectrometry (ICP-MS) is a popular method, and for identification of compounds via determination of molecular weight, electrospray ionization mass spectrometry (ESI-MS) is gaining increasing use. ICP-MS and ESI-MS, usually coupled to a separation technique such as chromatography or capillary electrophoresis, have already been applied to a large number of research problems in such diverse fields as environmental chemistry, nutritional science, and bioinorganic chemistry, but a great deal of work remains to be completed. Current areas of research to which ICP-MS and ESI-MS have been applied are discussed, and the existing instrumentation used to solve speciation problems is described.

DETERMINING SPECIATION OF PB IN PHOSPHATE AMENDED SOILS: METHOD LIMITATIONS

EPA Science Inventory

Determining the effectiveness of in-situ immobilization for P-amended, Pb-contaminated soils has typically relied on non-spectroscopic methods that in recent years have come under scrutiny due to technical and unforeseen error issues. In this study, we analyzed 18 soil samples vi...

Method to Select Metropolitan Areas of Epidemiologic Interest for Enhanced Air Quality Monitoring

EPA Science Inventory

The U.S. Environmental Protection Agency’s current Speciation Trends Network (STN) covers most major U.S. metropolitan areas and a wide range of particulate matter (PM) constituents and gaseous co-pollutants. However, using filter-based methods, most PM constituents are measured ...

Speciation of inorganic tellurium from seawater by ICP-MS following magnetic SPE separation and preconcentration.

PubMed

Huang, Chaozhang; Hu, Bin

2008-03-01

A new method was developed for the speciation of inorganic tellurium species in seawater by inductively coupled plasma-MS (ICP-MS) following selective magnetic SPE (MSPE) separation. Within the pH range of 2-9, tellurite (Te(IV)) could be quantitatively adsorbed on gamma-mercaptopropyltrimethoxysilane (gamma-MPTMS) modified silica-coated magnetic nanoparticles (MNPs), while the tellurate (Te(VI)) was not retained and remained in solution. Without filtration or centrifugation, these tellurite-loaded MNPs could be separated easily from the aqueous solution by simply applying external magnetic field. The Te(IV) adsorbed on the MNPs could be recovered quantitatively using a solution containing 2 mol/L HCl and 0.03 mol/L K2Cr2O7. Te(VI) was reduced to Te(IV) by L-cysteine prior to the determination of total tellurium, and its assay was based on subtracting Te(IV) from total tellurium. The parameters affecting the separation were investigated systematically and the optimal separation conditions were established. Under the optimal conditions, the LOD obtained for Te(IV) was 0.079 ng/L, while the precision was 7.0% (C = 10 ng/L, n = 7). The proposed method was successfully applied to the speciation of inorganic tellurium in seawater.

Selective speciation and determination of inorganic arsenic in water, food and biological samples.

PubMed

Tuzen, Mustafa; Saygi, Kadriye Ozlem; Karaman, Isa; Soylak, Mustafa

2010-01-01

A procedure for the speciation of arsenic(III) and arsenic(V) in natural water samples has been established in the presented work. Arsenic(III) ions were quantitatively recovered on Alternaria solani coated Diaion HP-2MG resin at pH 7, while the recoveries of arsenic(V) was below 10%. Arsenic(V) in the mixing solution containing As(III) and As(V) was reduced by using KI and L(+) ascorbic acid solution, then the procedure was applied to determination of total arsenic. Arsenic(V) was calculated as the difference between the total arsenic content and As(III) content. The determination of arsenic was performed by using hydride generation atomic absorption spectrometry. The influences of some alkali, earth alkali and transition metals on the biosorption of arsenic(III) were investigated. The preconcentration factor was 35. The detection limits for As(III) (N=20, k=3) was found as 11 ng L(-1). The relative standard deviation and relative error of the determinations were found to be lower than 7% and 4%, respectively. The accuracy of the method was confirmed with certified reference materials. The method was successively applied for the determination and speciation of inorganic arsenic in water, food and biological samples. Copyright 2009 Elsevier Ltd. All rights reserved.

Concentrations and speciation of arsenic in New England seaweed species harvested for food and agriculture.

PubMed

Taylor, Vivien F; Jackson, Brian P

2016-11-01

A survey of arsenic (As) concentrations and speciation was conducted on 10 species of seaweed from commercial harvesters and from collection at two sites in New England. Concentrations of As ranged from 4 to 106 mg/kg, mostly in the form of arsenosugars, with the distribution of arsenosugar analogs varying between taxa. In brown algae, As levels were correlated with phosphate concentrations, and arsenosugar speciation reflected differences in sulfur and phosphate concentrations between taxa. Several samples of the brown algae species Laminaria digitata contained significant levels of inorganic As (2.8-20 mg/kg), the most toxic form of As. A weak acid extraction with microwave heating was compared with a weaker methanol: water extraction method, and found to give slightly higher extraction efficiency with comparable relative concentrations of inorganic As, supporting the use of this faster and simpler extraction method for monitoring. Seaweed is a niche dietary item in the U.S. but its popularity is increasing; it is also used in agriculture and livestock farming which provide potential indirect routes for human exposure. The presence of occasional high concentrations of iAs, as well as the lack of toxicity studies on organic As species, suggest that monitoring of these high As foods is warranted. Copyright © 2016 Elsevier Ltd. All rights reserved.

Fractionation of Fe isotopes during granite weathering, soil formation, and plant uptake in an Alpine glacier forefield

NASA Astrophysics Data System (ADS)

Kretzschmar, R.; Kiczka, M.; Wiederhold, J. G.; Voegelin, A.; Kraemer, S.; Bourdon, B.

2010-12-01

Iron (Fe) is not only an essential element for almost all organisms, but is also involved in many biogeochemical processes including silicate weathering and soil formation. The aim of this study was to gain a better understanding of Fe isotope fractionation during initial silicate weathering and soil formation processes. Therefore, we investigated changes in Fe speciation and Fe isotope signatures in total soils and selected Fe pools along a weathering chronosequence within an Alpine glacier forefield on granite. The sampling sites along the dated chronosequence were deglaciated since up to 150 years, and we included two additional sites which were ice-free since several thousands of years. Changes in Fe speciation were investigated using Fe K-edge X-ray absorption spectroscopy (XAS) and also qualitatively documented by optical microscopy of soil thin sections. Iron in the unweathered rock was mainly present as structural Fe in biotite, with smaller amounts in chlorite, epidote, and magnetite. Within 150 years of deglaciation, the fraction of Fe(III) relative to total Fe increased from 34 to 53%, clearly documenting oxidation of Fe(II) in primary phyllosilicates. After 100 years of deglaciation, secondary Fe(III)-oxyhydroxides were detected by XAS and were also clearly evident in soil thin sections. Elemental analysis and Fe isotope analysis of particle size fractions by MC-ICP-MS showed that the clay fractions were significantly enriched in Fe and their δ56Fe signatures were up to 0.35‰ lower than those of the bulk soils (<2 mm). In addition, the hydroxylamine-hydrochloride extractable Fe pool (1 M HA-HCl in 25% acetic acid, pH 1.5), representing mainly poorly-crystalline Fe(III)-oxyhydroxides, increased with time of deglaciation and also had a significantly (by up to 0.7‰) lighter δ56Fe signature than the respective bulk soils. Thus, our data show that weathering of primary silicates, mainly biotite and chlorite, preferentially releases light Fe isotopes during oxidative weathering, which are subsequently enriched in secondary Fe(III)-oxyhydroxides with a rather constant isotopic offset of -0.7‰ in δ56Fe relative to the bulk soils. These findings are consistent with previous laboratory experiments on silicate weathering by proton- and ligand-promoted dissolution. The data suggest a kinetic isotope effect during Fe release from primary silicates, combined with quantitative oxidation and precipitation of Fe(III) as poorly-crystalline oxyhydroxides. Analysis of plants collected along the chronosequence revealed additional fractionation towards light Fe isotopes, but the plant contribution to total Fe cycling in this young ecosystem was still minor.

Particulate matter speciation profiles for light-duty gasoline vehicles in the United States.

PubMed

Sonntag, Darrell B; Baldauf, Richard W; Yanca, Catherine A; Fulper, Carl R

2014-05-01

Representative profiles for particulate matter particles less than or equal to 2.5 microm (PM2.5) are developed from the Kansas City Light-Duty Vehicle Emissions Study for use in the US. Environmental Protection Agency (EPA) vehicle emission model, the Motor Vehicle Emission Simulator (MOVES), and for inclusion in the EPA SPECIATE database for speciation profiles. The profiles are compatible with the inputs of current photochemical air quality models, including the Community Multiscale Air Quality Aerosol Module Version 6 (AE6). The composition of light-duty gasoline PM2.5 emissions differs significantly between cold start and hot stabilized running emissions, and between older and newer vehicles, reflecting both impacts of aging/deterioration and changes in vehicle technology. Fleet-average PM2.5 profiles are estimated for cold start and hot stabilized running emission processes. Fleet-average profiles are calculated to include emissions from deteriorated high-emitting vehicles that are expected to continue to contribute disproportionately to the fleet-wide PM2.5 emissions into the future. The profiles are calculated using a weighted average of the PM2.5 composition according to the contribution of PM2.5 emissions from each class of vehicles in the on-road gasoline fleet in the Kansas City Metropolitan Statistical Area. The paper introduces methods to exclude insignificant measurements, correct for organic carbon positive artifact, and control for contamination from the testing infrastructure in developing speciation profiles. The uncertainty of the PM2.5 species fraction in each profile is quantified using sampling survey analysis methods. The primary use of the profiles is to develop PM2.5 emissions inventories for the United States, but the profiles may also be used in source apportionment, atmospheric modeling, and exposure assessment, and as a basis for light-duty gasoline emission profiles for countries with limited data. PM2.5 speciation profiles were developed from a large sample of light-duty gasoline vehicles tested in the Kansas City area. Separate PM2.5 profiles represent cold start and hot stabilized running emission processes to distinguish important differences in chemical composition. Statistical analysis was used to construct profiles that represent PM2.5 emissions from the U.S. vehicle fleet based on vehicles tested from the 2005 calendar year Kansas City metropolitan area. The profiles have been incorporated into the EPA MOVES emissions model, as well as the EPA SPECIATE database, to improve emission inventories and provide the PM2.5 chemical characterization needed by CMAQv5.0 for atmospheric chemistry modeling.

Secondary sympatry caused by range expansion informs on the dynamics of microendemism in a biodiversity hotspot.

PubMed

Nattier, Romain; Grandcolas, Philippe; Elias, Marianne; Desutter-Grandcolas, Laure; Jourdan, Hervé; Couloux, Arnaud; Robillard, Tony

2012-01-01

Islands are bounded areas where high endemism is explained either by allopatric speciation through the fragmentation of the limited amount of space available, or by sympatric speciation and accumulation of daughter species. Most empirical evidence point out the dominant action of allopatric speciation. We evaluate this general view by looking at a case study where sympatric speciation is suspected. We analyse the mode, tempo and geography of speciation in Agnotecous, a cricket genus endemic to New Caledonia showing a generalized pattern of sympatry between species making sympatric speciation plausible. We obtained five mitochondrial and five nuclear markers (6.8 kb) from 37 taxa corresponding to 17 of the 21 known extant species of Agnotecous, and including several localities per species, and we conducted phylogenetic and dating analyses. Our results suggest that the diversification of Agnotecous occurred mostly through allopatric speciation in the last 10 Myr. Highly microendemic species are the most recent ones (<2 Myr) and current sympatry is due to secondary range expansion after allopatric speciation. Species distribution should then be viewed as a highly dynamic process and extreme microendemism only as a temporary situation. We discuss these results considering the influence of climatic changes combined with intricate soil diversity and mountain topography. A complex interplay between these factors could have permitted repeated speciation events and range expansion.

Sulfur K-edge XANES and acid volatile sulfide analyses of changes in chemical speciation of S and Fe during sequential extraction of trace metals in anoxic sludge from biogas reactors.

PubMed

Shakeri Yekta, Sepehr; Gustavsson, Jenny; Svensson, Bo H; Skyllberg, Ulf

2012-01-30

The effect of sequential extraction of trace metals on sulfur (S) speciation in anoxic sludge samples from two lab-scale biogas reactors augmented with Fe was investigated. Analyses of sulfur K-edge X-ray absorption near edge structure (S XANES) spectroscopy and acid volatile sulfide (AVS) were conducted on the residues from each step of the sequential extraction. The S speciation in sludge samples after AVS analysis was also determined by S XANES. Sulfur was mainly present as FeS (≈ 60% of total S) and reduced organic S (≈ 30% of total S), such as organic sulfide and thiol groups, in the anoxic solid phase. Sulfur XANES and AVS analyses showed that during first step of the extraction procedure (the removal of exchangeable cations), a part of the FeS fraction corresponding to 20% of total S was transformed to zero-valent S, whereas Fe was not released into the solution during this transformation. After the last extraction step (organic/sulfide fraction) a secondary Fe phase was formed. The change in chemical speciation of S and Fe occurring during sequential extraction procedure suggests indirect effects on trace metals associated to the FeS fraction that may lead to incorrect results. Furthermore, by S XANES it was verified that the AVS analysis effectively removed the FeS fraction. The present results identified critical limitations for the application of sequential extraction for trace metal speciation analysis outside the framework for which the methods were developed. Copyright © 2011 Elsevier B.V. All rights reserved.

Ultrasensitive Speciation Analysis of Mercury in Rice by Headspace Solid Phase Microextraction Using Porous Carbons and Gas Chromatography-Dielectric Barrier Discharge Optical Emission Spectrometry.

PubMed

Lin, Yao; Yang, Yuan; Li, Yuxuan; Yang, Lu; Hou, Xiandeng; Feng, Xinbin; Zheng, Chengbin

2016-03-01

Rice consumption is a primary pathway for human methylmercury (MeHg) exposure in inland mercury mining areas of Asia. In addition, the use of iodomethane, a common fumigant that significantly accelerates the methylation of mercury in soil under sunlight, could increase the MeHg exposure from rice. Conventional hyphenated techniques used for mercury speciation analysis are usually too costly for most developing countries. Consequently, there is an increased interest in the development of sensitive and inexpensive methods for the speciation of mercury in rice. In this work, gas chromatography (GC) coupled to dielectric barrier discharge optical emission spectrometry (DBD-OES) was developed for the speciation analysis of mercury in rice. Prior to GC-DBD-OES analysis, mercury species were derivatized to their volatile species with NaBPh4 and preconcentrated by headspace solid phase microextraction using porous carbons. Limits of detection of 0.5 μg kg(-1) (0.16 ng), 0.75 μg kg(-1) (0.24 ng), and 1.0 μg kg(-1) (0.34 ng) were obtained for Hg(2+), CH3Hg(+), and CH3CH2Hg(+), respectively, with relative standard deviations (RSDs) better than 5.2% and 6.8% for one fiber or fiber-to-fiber mode, respectively. Recoveries of 90-105% were obtained for the rice samples, demonstrating the applicability of the proposed technique. Owing to the small size, low power, and low gas consumption of DBD-OES as well as efficient extraction of mercury species by porous carbons headspace solid phase micro-extraction, the proposed technique provides several advantages including compactness, cost-effectiveness, and potential to couple with miniature GC to accomplish the field speciation of mercury in rice compared to conventional hyphenated techniques.

Effects of water management on arsenic and cadmium speciation and accumulation in an upland rice cultivar.

PubMed

Hu, Pengjie; Ouyang, Younan; Wu, Longhua; Shen, Libo; Luo, Yongming; Christie, Peter

2015-01-01

Pot and field experiments were conducted to investigate the effects of water regimes on the speciation and accumulation of arsenic (As) and cadmium (Cd) in Brazilian upland rice growing in soils polluted with both As and Cd. In the pot experiment constant and intermittent flooding treatments gave 3-16 times higher As concentrations in soil solution than did aerobic conditions but Cd showed the opposite trend. Compared to arsenate, there were more marked changes in the arsenite concentrations in the soil solution as water management shifted, and therefore arsenite concentrations dominated the As speciation and bioavailability in the soil. In the field experiment As concentrations in the rice grains increased from 0.14 to 0.21 mg/kg while Cd concentrations decreased from 0.21 to 0.02 mg/kg with increasing irrigation ranging from aerobic to constantly flooding conditions. Among the various water regimes the conventional irrigation treatment produced the highest rice grain yield of 6.29 tons/ha. The As speciation analysis reveals that the accumulation of dimethylarsinic acid (from 11.3% to 61.7%) made a greater contribution to the increase in total As in brown rice in the intermittent and constant flooding treatments compared to the intermittent-aerobic treatment. Thus, water management exerted opposite effects on Cd and As speciation and bioavailability in the soil and consequently on their accumulation in the upland rice. Special care is required when irrigation regime methods are employed to mitigate the accumulation of metal(loid)s in the grain of rice grown in soils polluted with both As and Cd. Copyright © 2014. Published by Elsevier B.V.

Occurrence and Speciation of Polymeric Chromium(III), Monomeric Chromium(III) and Chromium(VI) in Environmental Samples

PubMed Central

HU, LIGANG; CAI, YONG; JIANG, GUIBIN

2016-01-01

Laboratory experiments suggest that polymeric Cr(III) could exist in aqueous solution for a relative long period of time. However, the occurrence of polymeric Cr(III) has not been reported in environmental media due partially to the lack of method for speciating polymeric Cr. We observed an unknown Cr species during the course of study on speciation of Cr in the leachates of chromated-copper-arsenate (CCA)-treated wood. Efforts were made to identify structure of the unknown Cr species. Considering the forms of Cr existed in the CCA-treated woods, we mainly focused our efforts to determine if the unknown species were polymeric Cr(III), complex of Cr/As or complex of Cr with dissolved organic matter (DOM). In order to evaluate whether polymeric Cr(III) largely exist in wood leachates, high performance liquid chromatography coupled with inductively coupled mass spectrometry (HPLC-ICPMS was used) for simultaneous speciation of monomeric Cr(III), polymeric Cr(III), and Cr(VI). In addition to wood leachates where polymeric Cr (III) ranged from 39.1 to 67.4 %, occurrence of the unknown Cr species in other environmental matrices, including surface waters, tap and waste waters, was also investigated. It was found that polymeric Cr(III) could exist in environmental samples containing μg/L level of Cr, at a level up to 60% of total Cr, suggesting that polymeric Cr(III) could significantly exist in natural environments. Failure in quantifying polymeric Cr(III) would lead to the underestimation of total Cr and bias in Cr speciation. The environmental implication of the presence of polymeric Cr(III) species in the environment deserves further study. PMID:27156211

A comparative analysis of island floras challenges taxonomy-based biogeographical models of speciation.

PubMed

Igea, Javier; Bogarín, Diego; Papadopulos, Alexander S T; Savolainen, Vincent

2015-02-01

Speciation on islands, and particularly the divergence of species in situ, has long been debated. Here, we present one of the first, complete assessments of the geographic modes of speciation for the flora of a small oceanic island. Cocos Island (Costa Rica) is pristine; it is located 550 km off the Pacific coast of Central America. It harbors 189 native plant species, 33 of which are endemic. Using phylogenetic data from insular and mainland congeneric species, we show that all of the endemic species are derived from independent colonization events rather than in situ speciation. This is in sharp contrast to the results of a study carried out in a comparable system, Lord Howe Island (Australia), where as much as 8.2% of the plant species were the product of sympatric speciation. Differences in physiography and age between the islands may be responsible for the contrasting patterns of speciation observed. Importantly, comparing phylogenetic assessments of the modes of speciation with taxonomy-based measures shows that widely used island biogeography approaches overestimate rates of in situ speciation. © 2014 The Author(s). Evolution © 2014 The Society for the Study of Evolution.

Identification of novel peptides for horse meat speciation in highly processed foodstuffs.

PubMed

Claydon, Amy J; Grundy, Helen H; Charlton, Adrian J; Romero, M Rosario

2015-01-01

There is a need for robust analytical methods to support enforcement of food labelling legislation. Proteomics is emerging as a complementary methodology to existing tools such as DNA and antibody-based techniques. Here we describe the development of a proteomics strategy for the determination of meat species in highly processed foods. A database of specific peptides for nine relevant animal species was used to enable semi-targeted species determination. This principle was tested for horse meat speciation, and a range of horse-specific peptides were identified as heat stable marker peptides for the detection of low levels of horse meat in mixtures with other species.

Speciation of inorganic arsenic in drinking water by wavelength-dispersive X-ray fluorescence spectrometry after in situ preconcentration with miniature solid-phase extraction disks.

PubMed

Hagiwara, Kenta; Inui, Tetsuo; Koike, Yuya; Aizawa, Mamoru; Nakamura, Toshihiro

2015-03-01

A rapid and simple method using wavelength-dispersive X-ray fluorescence (WDXRF) spectrometry after in situ solid-phase extraction (SPE) was developed for the speciation and evaluation of the concentration of inorganic arsenic (As) in drinking water. The method involves the simultaneous collection of As(III) and As(V) using 13 mm ϕ SPE miniature disks. The removal of Pb(2+) from the sample water was first conducted to avoid the overlapping PbLα and AsKα spectra on the XRF spectrum. To this end, a 50 mL aqueous sample (pH 5-9) was passed through an iminodiacetate chelating disk. The filtrate was adjusted to pH 2-3 with HCl, and then ammonium pyrrolidine dithiocarbamate solution was added. The solution was passed through a hydrophilic polytetrafluoroethylene filter placed on a Zr and Ca loaded cation-exchange disk at a flow rate of 12.5 mL min(-1) to separate As(III)-pyrrolidine dithiocarbamate complex and As(V). Each SPE disk was affixed to an acrylic plate using adhesive cellophane tape, and then examined by WDXRF spectrometry. The detection limits of As(III) and As(V) were 0.8 and 0.6 μg L(-1), respectively. The proposed method was successfully applied to screening for As speciation and concentration evaluation in spring water and well water. Copyright © 2014 Elsevier B.V. All rights reserved.

EVALUATION OF EXTRACTION AND SPECTROSCOPIC METHODS FOR PB SPECIATION IN AN AMENDED SOIL

EPA Science Inventory

Immobilization of pyromorphite (Pbs(PO4hCI) via P amendments to Pb contaminated soils is proving to be a viable method of remediation. However, the issue of ascertaining the amount of soil Pb converted to pyromorphite is difficult in heterogeneous soil systems. Previous attempts ...

ADVANCED EMISSIONS SPECIATION METHODOLOGIES FOR THE AUTO/OIL AIR QUALITY IMPROVEMENT RESEARCH PROGRAM - II. ALDEHYDES, KETONES, AND ALCOHOLS

EPA Science Inventory

Analytical methods for determining individual aldehyde, ketone, and alcohol emissions from gasoline-, methanol-, and variable-fueled vehicles are described. These methods were used in the Auto/Oil Air quality Improvement Research Program to provide emission data for comparison of...

Sulfur and iron speciation in gas-rich impact-melt glasses from basaltic shergottites determined by microXANES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sutton, S.R.; Rao, M.N.; Nyquist, L.E.

2008-04-28

Sulfur and iron K XANES measurements were made on GRIM glasses from EET 79001. Iron is in the ferrous state. Sulfur speciation is predominately sulfide coordination but is Fe coordinated in Lith B and, most likely, Ca coordinated in Lith A. Sulfur is abundantly present as sulfate near Martian surface based on chemical and mineralogical investigations on soils and rocks in Viking, Pathfinder and MER missions. Jarosite is identified by Moessbauer studies on rocks at Meridian and Gusev, whereas MgSO{sub 4} is deduced from MgO-SO{sub 3} correlations in Pathfinder MER and Viking soils. Other sulfate minerals such as gypsum andmore » alunogen/S-rich aluminosilicates and halides are detected only in martian meteorites such as shergottites and nakhlites using SEM/FE-SEM and EMPA techniques. Because sulfur has the capacity to occur in multiple valence states, determination of sulfur speciation (sulfide/sulfate) in secondary mineral assemblages in soils and rocks near Mars surface may help us understand whether the fluid-rock interactions occurred under oxidizing or reducing conditions. On Earth, volcanic rocks contain measurable quantities of sulfur present as both sulfide and sulfate. Carroll and Rutherford showed that oxidized forms of sulfur may comprise a significant fraction of total dissolved sulfur, if the oxidation state is higher than {approx}2 log fO{sub 2} units relative to the QFM buffer. Terrestrial samples containing sulfates up to {approx}25% in fresh basalts from the Galapagos Rift on one hand and high sulfide contents present in oceanic basalts on the other indicate that the relative abundance of sulfide and sulfate varies depending on the oxygen fugacity of the system. Basaltic shergottites (bulk) such as Shergotty, EET79001 and Zagami usually contain small amounts of sulfur ({approx}0.5%) as pyrrhotite. But, in isolated glass pockets containing secondary salts (known as GRIM glasses) in these meteorites, sulfur is present in high abundance ({approx}1-12%). To determine sulfur speciation (sulfide, sulfate or elemental sulfur) in these glasses, Gooding et al. and Burgess et al. carried out vacuum pyrolysis experiments on these GRIM glasses (also called Lith C) using quadrupole mass-spectrometric methods. They found that the evolved S-bearing gases from these samples consisted of both SO{sub 2} (from sulfate) and H{sub 2}S (from sulfide) in varying proportions. However, as mass-spectrometric studies do not provide details about spatial association of these S-species in these samples, we have studied the spatial distribution of sulfides and sulfates in GRIM glasses using sulfur K micro-XANES techniques in the present study. The microscale speciation of S may have important implications for the Rb-Sr isotope systematics of EET79001 Lith C glasses. In reference to oxidative weathering of surface basalts on Mars yielding secondary iron sulfates, Solberg and Burns examined a GRIM glass in EET79001 by Moessbauer spectroscopic techniques and showed that the percentage of Fe{sup 3+} in Lith C is <2%. They suggested that the Lith C contains very little Fe{sup 3+} despite the occurrence of oxidized sulfate in them, indicating that the conditions leading to the formation of these glasses were insufficiently oxidizing to produce Fe{sup 3+} from Fe{sup 2+} in these glasses. To understand the implications of these observations for the formation of the GRIM glasses, we determined the oxidation state of Fe in the GRIM glasses using Fe K micro-XANES techniques. The S and Fe K micro-XANES measurements were performed on thin sections from EET79001: 506 from Lith A and 507 from Lith B.« less

Chemical speciation of heavy metals by surface-enhanced Raman scattering spectroscopy: identification and quantification of inorganic- and methyl-mercury in water

NASA Astrophysics Data System (ADS)

Guerrini, Luca; Rodriguez-Loureiro, Ignacio; Correa-Duarte, Miguel A.; Lee, Yih Hong; Ling, Xing Yi; García de Abajo, F. Javier; Alvarez-Puebla, Ramon A.

2014-06-01

Chemical speciation of heavy metals has become extremely important in environmental and analytical research because of the strong dependence that toxicity, environmental mobility, persistence and bioavailability of these pollutants have on their specific chemical forms. Novel nano-optical-based detection strategies, capable of overcoming the intrinsic limitations of well-established analytic methods for the quantification of total metal ion content, have been reported, but the speciation of different chemical forms has not yet been achieved. Here, we report the first example of a SERS-based sensor for chemical speciation of toxic metal ions in water at trace levels. Specifically, the inorganic Hg2+ and the more toxicologically relevant methylmercury (CH3Hg+) are selected as analytical targets. The sensing platform consists of a self-assembled monolayer of 4-mercaptopyridine (MPY) on highly SERS-active and robust hybrid plasmonic materials formed by a dense layer of interacting gold nanoparticles anchored onto polystyrene microbeads. The co-ordination of Hg2+ and CH3Hg+ to the nitrogen atom of the MPY ring yields characteristic changes in the vibrational SERS spectra of the organic chemoreceptor that can be qualitatively and quantitatively correlated to the presence of the two different mercury forms.Chemical speciation of heavy metals has become extremely important in environmental and analytical research because of the strong dependence that toxicity, environmental mobility, persistence and bioavailability of these pollutants have on their specific chemical forms. Novel nano-optical-based detection strategies, capable of overcoming the intrinsic limitations of well-established analytic methods for the quantification of total metal ion content, have been reported, but the speciation of different chemical forms has not yet been achieved. Here, we report the first example of a SERS-based sensor for chemical speciation of toxic metal ions in water at trace levels. Specifically, the inorganic Hg2+ and the more toxicologically relevant methylmercury (CH3Hg+) are selected as analytical targets. The sensing platform consists of a self-assembled monolayer of 4-mercaptopyridine (MPY) on highly SERS-active and robust hybrid plasmonic materials formed by a dense layer of interacting gold nanoparticles anchored onto polystyrene microbeads. The co-ordination of Hg2+ and CH3Hg+ to the nitrogen atom of the MPY ring yields characteristic changes in the vibrational SERS spectra of the organic chemoreceptor that can be qualitatively and quantitatively correlated to the presence of the two different mercury forms. Electronic supplementary information (ESI) available: Representative TEM and ESEM images of AuNPs and PS@Au particles. Optical extinction spectra of AuNPs and PS@Au suspensions. SERS spectra of unmodified PS@Au suspension before and after the addition of CH3Hg+. SERS spectra of PS@Au-MPY upon addition of several metal solutions. Detailed SERS study of the MPY response to high concentration of CH3Hg+. See DOI: 10.1039/c4nr01464b

Loss of sexual recombination and segregation is associated with increased diversification in evening primroses.

PubMed

Johnson, Marc T J; Fitzjohn, Richard G; Smith, Stacey D; Rausher, Mark D; Otto, Sarah P

2011-11-01

The loss of sexual recombination and segregation in asexual organisms has been portrayed as an irreversible process that commits asexually reproducing lineages to reduced diversification. We test this hypothesis by estimating rates of speciation, extinction, and transition between sexuality and functional asexuality in the evening primroses. Specifically, we estimate these rates using the recently developed BiSSE (Binary State Speciation and Extinction) phylogenetic comparative method, which employs maximum likelihood and Bayesian techniques. We infer that net diversification rates (speciation minus extinction) in functionally asexual evening primrose lineages are roughly eight times faster than diversification rates in sexual lineages, largely due to higher speciation rates in asexual lineages. We further reject the hypothesis that a loss of recombination and segregation is irreversible because the transition rate from functional asexuality to sexuality is significantly greater than zero and in fact exceeded the reverse rate. These results provide the first empirical evidence in support of the alternative theoretical prediction that asexual populations should instead diversify more rapidly than sexual populations because they are free from the homogenizing effects of sexual recombination and segregation. Although asexual reproduction may often constrain adaptive evolution, our results show that the loss of recombination and segregation need not be an evolutionary dead end in terms of diversification of lineages. © 2011 The Author(s). Evolution© 2011 The Society for the Study of Evolution.

Evolution of sulfur speciation in bitumen through hydrous pyrolysis induced thermal maturation of Jordanian Ghareb Formation oil shale

USGS Publications Warehouse

Birdwell, Justin E.; Lewan, Michael; Bake, Kyle D.; Bolin, Trudy B.; Craddock, Paul R.; Forsythe, Julia C.; Pomerantz, Andrew E.

2018-01-01

Previous studies on the distribution of bulk sulfur species in bitumen before and after artificial thermal maturation using various pyrolysis methods have indicated that the quantities of reactive (sulfide, sulfoxide) and thermally stable (thiophene) sulfur moieties change following consistent trends under increasing thermal stress. These trends show that sulfur distributions change during maturation in ways that are similar to those of carbon, most clearly illustrated by the increase in aromatic sulfur (thiophenic) as a function of thermal maturity. In this study, we have examined the sulfur moiety distributions of retained bitumen from a set of pre- and post-pyrolysis rock samples in an organic sulfur-rich, calcareous oil shale from the Upper Cretaceous Ghareb Formation. Samples collected from outcrop in Jordan were subjected to hydrous pyrolysis (HP). Sulfur speciation in extracted bitumens was examined using K-edge X-ray absorption near-edge structure (XANES) spectroscopy. The most substantial changes in sulfur distribution occurred at temperatures up to the point of maximum bitumen generation (∼300 °C) as determined from comparison of the total organic carbon content for samples before and after extraction. Organic sulfide in bitumen decreased with increasing temperature at relatively low thermal stress (200–300 °C) and was not detected in extracts from rocks subjected to HP at temperatures above around 300 °C. Sulfoxide content increased between 200 and 280 °C, but decreased at higher temperatures. The concentration of thiophenic sulfur increased up to 300 °C, and remained essentially stable under increasing thermal stress (mg-S/g-bitumen basis). The ratio of stable-to-reactive+stable sulfur moieties ([thiophene/(sulfide+sulfoxide+thiophene)], T/SST) followed a sigmoidal trend with HP temperature, increasing slightly up to 240 °C, followed by a substantial increase between 240 and 320 °C, and approaching a constant value (∼0.95) at temperatures above 320 °C. This sulfur moiety ratio appears to provide complementary thermal maturity information to geochemical parameters derived from other analyses of extracted source rocks.

The long-term environmental impacts of the Mount Polley mine tailings spill, British Columbia, Canada

NASA Astrophysics Data System (ADS)

Byrne, Patrick; Hudson-Edwards, Karen; Macklin, Mark; Brewer, Paul; Bird, Graham; Williams, Richard

2015-04-01

On the 4th August 2014 a tailings impoundment failure at the Mount Polley gold and copper mine in British Columbia, Canada, released approximately 25 million m3 of solid and liquid waste into Hazeltine Creek, Quesnel Lake and Polley Lake. The sheer volume of the tailings released caused Haseltine Creek channel to expand from 2m to over 25m in width and Polley Lake water level to rise by 1.7m. The spill also removed trees in a 900 km2 corridor either side of Hazeltine Creek. Local residents and government officials have expressed serious concerns regarding the potential long-term effects on regional biodiversity, water security and to the livelihoods of First Nation communities. Among impoundment failures, the Mount Polley disaster is unique in that the solid tailings contain an unusual mixture of metal contaminants (arsenic, copper, gold, manganese, nickel, lead, vanadium). As particulate matter is the principal carrier of metal contaminants, the spilled tailings may reside in the regional soils and sediments for 1000s of years serving as a secondary source of pollution. The environmental risk posed by the spilled tailings is compounded by the location of the spill in a mountainous forested catchment, affected by severe winters with prominent spring snow melts that have the potential to remobilise very large quantities of spilled tailings. No data currently exist on the short- to long-term behaviour of these tailings in soils and sediments and the effects of the clean-up operations on their behaviour in this type of river environment. In this study, we adopt a multidisciplinary approach to determine the environmental and geomorphological impacts of the tailings spill. We have two specific objectives. (1) The physicochemical speciation and geochemical stability of spilled tailings will be characterised in surface and hyporheic sediments using bulk chemistry, mineralogical (XRD and SEM) and speciation methods (sequential extractions, electron microprobe analysis, XAS). (2) Pre- and post-remediation geomorphological assessments will use unmanned aerial vehicle (UAV) photographic surveys and ground-based topographic surveys to (i) establish the efficacy of remediation efforts in stabilising Hazeltine Creek channel and (ii) quantify the physical remobilisation of tailings during the spring snowmelt.

The reality and importance of founder speciation in evolution.

PubMed

Templeton, Alan R

2008-05-01

A founder event occurs when a new population is established from a small number of individuals drawn from a large ancestral population. Mayr proposed that genetic drift in an isolated founder population could alter the selective forces in an epistatic system, an observation supported by recent studies. Carson argued that a period of relaxed selection could occur when a founder population is in an open ecological niche, allowing rapid population growth after the founder event. Selectable genetic variation can actually increase during this founder-flush phase due to recombination, enhanced survival of advantageous mutations, and the conversion of non-additive genetic variance into additive variance in an epistatic system, another empirically confirmed prediction. Templeton combined the theories of Mayr and Carson with population genetic models to predict the conditions under which founder events can contribute to speciation, and these predictions are strongly confirmed by the empirical literature. Much of the criticism of founder speciation is based upon equating founder speciation to an adaptive peak shift opposed by selection. However, Mayr, Carson and Templeton all modeled a positive interaction of selection and drift, and Templeton showed that founder speciation is incompatible with peak-shift conditions. Although rare, founder speciation can have a disproportionate importance in adaptive innovation and radiation, and examples are given to show that "rare" does not mean "unimportant" in evolution. Founder speciation also interacts with other speciation mechanisms such that a speciation event is not a one-dimensional process due to either selection alone or drift alone. (c) 2008 Wiley Periodicals, Inc.

CuO and ZnO nanoparticles: phytotoxicity, metal speciation, and induction of oxidative stress in sand-grown wheat

NASA Astrophysics Data System (ADS)

Dimkpa, Christian O.; McLean, Joan E.; Latta, Drew E.; Manangón, Eliana; Britt, David W.; Johnson, William P.; Boyanov, Maxim I.; Anderson, Anne J.

2012-09-01

Metal oxide nanoparticles (NPs) are reported to impact plant growth in hydroponic systems. This study describes the impact of commercial CuO (<50 nm) and ZnO (<100 nm) NPs on wheat ( Triticum aestivum) grown in a solid matrix, sand. The NPs contained both metallic and non-metallic impurities to different extents. Dynamic light scattering and atomic force microscopy (AFM) assessments confirmed aggregation of the NPs to submicron sizes. AFM showed transformation of ZnO NPs from initial rhomboid shapes in water to elongated rods in the aqueous phase of the sand matrix. Solubilization of metals occurred in the sand at similar rates from CuO or ZnO NPs as their bulk equivalents. Amendment of the sand with 500 mg Cu and Zn/kg sand from the NPs significantly ( p = 0.05) reduced root growth, but only CuO NPs impaired shoot growth; growth reductions were less with the bulk amendments. Dissolved Cu from CuO NPs contributed to their phytotoxicity but Zn release did not account for the changes in plant growth. Bioaccumulation of Cu, mainly as CuO and Cu(I)-sulfur complexes, and Zn as Zn-phosphate was detected in the shoots of NP-challenged plants. Total Cu and Zn levels in shoot were similar whether NP or bulk materials were used. Oxidative stress in the NP-treated plants was evidenced by increased lipid peroxidation and oxidized glutathione in roots and decreased chlorophyll content in shoots; higher peroxidase and catalase activities were present in roots. These findings correlate with the NPs causing increased production of reactive oxygen species. The accumulation of Cu and Zn from NPs into edible plants has relevance to the food chain.

Speciation in birds: genes, geography, and sexual selection.

PubMed

Edwards, Scott V; Kingan, Sarah B; Calkins, Jennifer D; Balakrishnan, Christopher N; Jennings, W Bryan; Swanson, Willie J; Sorenson, Michael D

2005-05-03

Molecular studies of speciation in birds over the last three decades have been dominated by a focus on the geography, ecology, and timing of speciation, a tradition traceable to Mayr's Systematics and the Origin of Species. However, in the recent years, interest in the behavioral and molecular mechanisms of speciation in birds has increased, building in part on the older traditions and observations from domesticated species. The result is that many of the same mechanisms proffered for model lineages such as Drosophila--mechanisms such as genetic incompatibilities, reinforcement, and sexual selection--are now being seriously entertained for birds, albeit with much lower resolution. The recent completion of a draft sequence of the chicken genome, and an abundance of single-nucleotide polymorphisms on the autosomes and sex chromosomes, will dramatically accelerate research on the molecular mechanisms of avian speciation over the next few years. The challenge for ornithologists is now to inform well studied examples of speciation in nature with increased molecular resolution-to clone speciation genes if they exist--and thereby evaluate the relative roles of extrinsic, intrinsic, deterministic, and stochastic causes for avian diversification.

Atmospheric speciation of mercury in two contrasting Southeastern US airsheds

NASA Astrophysics Data System (ADS)

Gabriel, Mark C.; Williamson, Derek G.; Brooks, Steve; Lindberg, Steve

Simultaneous measurement of gaseous elemental, reactive gaseous, and fine particulate mercury took place in Tuscaloosa AL, (urban airshed) and Cove Mountain, TN (non-urban airshed) during the summers of 2002 and 2003. The objective of this research was to (1) summarize the temporal distribution of each mercury specie at each site and compare to other speciation data sets developed by other researchers and (2) provide insight into urban and non-urban mercury speciation effects using various statistical methods. Average specie concentrations were as follows: 4.05 ng m -3 (GEM), 13.6 pg m -3 (RGM), 16.4 pg m -3 (Hg-p) for Tuscaloosa; 3.20 ng m -3 (GEM), 13.6 pg m -3 (RGM), 9.73 pg m -3 (Hg-p) for Cove Mountain. As a result of urban airshed impacts, short periods of high concentration for all mercury species was common in Tuscaloosa. At Cove Mountain a consistent mid-day rise and evening drop for mercury species was found. This pattern was primarily the result of un-impacted physical boundary layer movement, although, other potential impacts were ambient photochemistry and air-surface exchange of mercury. Meteorological parameters that are known to heavily impact mercury speciation were similar for the study period for Tuscaloosa and Cove Mountain except for wind speed (m s -1), which was higher at Cove Mountain. For both sites statistically significant ( p<0.0001), inverse relationships existed between wind speed and Hg 0 concentration. A weaker windspeed-Hg 0 correlation existed for Tuscaloosa. By analyzing Hg concentration—wind speed magnitude change at both sites it was found that wind speed at Cove Mountain had a greater influence on Hg 0 concentration variability than Tuscaloosa by a factor of 3. Using various statistical tests, we concluded that the nature of Tuscaloosa's atmospheric mercury speciation was the result of typical urban airshed impacts. Cove Mountain showed atmospheric mercury speciation characteristics indicative of a non-urban area along with potential influence from steady regional input of mercury pollution from larger sources.

Rates of speciation in the fossil record

NASA Technical Reports Server (NTRS)

Sepkoski, J. J. Jr; Sepkoski JJ, J. r. (Principal Investigator)

1998-01-01

Data from palaeontology and biodiversity suggest that the global biota should produce an average of three new species per year. However, the fossil record shows large variation around this mean. Rates of origination have declined through the Phanerozoic. This appears to have been largely a function of sorting among higher taxa (especially classes), which exhibit characteristic rates of speciation (and extinction) that differ among them by nearly an order of magnitude. Secular decline of origination rates is hardly constant, however; many positive deviations reflect accelerated speciation during rebounds from mass extinctions. There has also been general decline in rates of speciation within major taxa through their histories, although rates have tended to remain higher among members in tropical regions. Finally, pulses of speciation appear sometimes to be associated with climate change, although moderate oscillations of climate do not necessarily promote speciation despite forcing changes in species' geographical ranges.

Speciation driven by hybridization and chromosomal plasticity in a wild yeast.

PubMed

Leducq, Jean-Baptiste; Nielly-Thibault, Lou; Charron, Guillaume; Eberlein, Chris; Verta, Jukka-Pekka; Samani, Pedram; Sylvester, Kayla; Hittinger, Chris Todd; Bell, Graham; Landry, Christian R

2016-01-11

Hybridization is recognized as a powerful mechanism of speciation and a driving force in generating biodiversity. However, only few multicellular species, limited to a handful of plants and animals, have been shown to fulfil all the criteria of homoploid hybrid speciation. This lack of evidence could lead to the interpretation that speciation by hybridization has a limited role in eukaryotes, particularly in single-celled organisms. Laboratory experiments have revealed that fungi such as budding yeasts can rapidly develop reproductive isolation and novel phenotypes through hybridization, showing that in principle homoploid speciation could occur in nature. Here, we report a case of homoploid hybrid speciation in natural populations of the budding yeast Saccharomyces paradoxus inhabiting the North American forests. We show that the rapid evolution of chromosome architecture and an ecological context that led to secondary contact between nascent species drove the formation of an incipient hybrid species with a potentially unique ecological niche.

Dispersive micro-solid phase extraction combined with dispersive liquid-liquid microextraction for speciation analysis of antimony by electrothermal vaporization inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Chen, Shizhong; Zhu, Shengping; Lu, Dengbo

2018-01-01

A method was developed for speciation analysis of antimony by electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) after preconcentration/separation using dispersive micro-solid phase extraction (DMSPE) and dispersive liquid-liquid micro-extraction (DLLME). In DMSPE, titanium dioxide nanofibers were used for preconcentration and separation of analytes. The upper aqueous phase and elution solution from DMSPE were used for further preconcentration and separation of Sb(III) and Sb(V) by DLLME without any pre-oxidation or pre-reduction operation, respectively. The extracts from DLLME were used for ETV-ICP-MS determination with APDC as a chemical modifier. Under optimal conditions, the detection limits of this method were 0.019 and 0.025 pg mL- 1 with relative standard deviations of 5.7% and 6.9% for Sb(III) and Sb(V) (c = 1.0 ng mL- 1, n = 9), respectively. This method was applied for speciation analysis of Sb and its distribution in the tea leaves and the tea infusion, including total, suspended, soluble, organic and inorganic Sb as well as Sb(III) and Sb(V). The results showed that the contents of Sb are 62.7, 12.9 and 47.3 ng g- 1 in the tea leaves, tea residue and tea soup, respectively; those of soluble, organic, inorganic, Sb(III) and Sb(V) are 0.41, 0.11, 0.29, 0.21 and 0.07 ng mL- 1 in the tea soup, respectively. A certified reference material of tea leaves (GBW 07605) was analyzed by this method with satisfactory results.

Speciation of chromium using reversed phase-high performance liquid chromatography coupled to different spectrometric detection methods

NASA Astrophysics Data System (ADS)

Andrle, C. M.; Jakubowski, N.; Broekaert, J. A. C.

1997-02-01

Speciation of Cr(III) and Cr(VI) based on the formation of different complexes with ammonium-pyrrolidinedithioate (APDC) in a continuous flow technique and their preconcentration using solid phase extraction (SPE) have been elaborated and applied to the analysis of waste waters from the galvanic industry. The Cr complexes were separated and determined using reversed phase-high performance liquid chromatography (RP-HPLC) coupled to different detection methods, namely UV-detection, graphite furnace-atomic absorption spectrometry (GF-AAS) and inductively coupled plasma mass spectrometry with hydraulic high pressure nebulization (HHPN/ICP-MS). After optimization the detection limits for Cr(III) and Cr(VI) of all methods are at the μg 1 -1 level and the precision in terms of RSD is 5% ( cCr = 100 μg 1 -1, N = 10). The procedure was applied to the determination of Cr(III) and Cr(VI) at the μg 1 -1 level in galvanic waste waters, and its accuracy was approved by comparing the results with those of independent methods.

Speciation and Attenuation of Arsenic and Selenium at Coal Combustion By-Product Management Facilities

DOE Office of Scientific and Technical Information (OSTI.GOV)

K. Ladwig

2005-12-31

The overall objective of this project was to evaluate the impact of key constituents captured from power plant air streams (principally arsenic and selenium) on the disposal and utilization of coal combustion products (CCPs). Specific objectives of the project were: (1) to develop a comprehensive database of field leachate concentrations at a wide range of CCP management sites, including speciation of arsenic and selenium, and low-detection limit analyses for mercury; (2) to perform detailed evaluations of the release and attenuation of arsenic species at three CCP sites; and (3) to perform detailed evaluations of the release and attenuation of seleniummore » species at three CCP sites. Each of these objectives was accomplished using a combination of field sampling and laboratory analysis and experimentation. All of the methods used and results obtained are contained in this report. For ease of use, the report is subdivided into three parts. Volume 1 contains methods and results for the field leachate characterization. Volume 2 contains methods and results for arsenic adsorption. Volume 3 contains methods and results for selenium adsorption.« less

ARSENIC REMOVAL

EPA Science Inventory

Presentation covered five topics; arsenic chemistry, best available technology (BAT), surface water technology, ground water technology and case studies of arsenic removal. The discussion on arsenic chemistry focused on the need and method of speciation for AsIII and AsV. BAT me...

In Situ NMR Observation of the Temporal Speciation of Lithium Sulfur Batteries during Electrochemical Cycling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Hao; Sa, Niya; He, Meinan

The understanding of the reaction mechanism and temporal speciation of the lithium sulfur batteries is challenged by complex polysulfide disproportionation chemistry coupled with the precipitation and dissolution of species. In this report, for the first time, we present a comprehensive method to investigate lithium sulfur electrochemistry using in situ 7Li NMR spectroscopy, a technique that is capable of quantitatively capturing the evolution of the soluble and precipitated lithium (poly)sulfides during electrochemical cycling. Furthermore, through deconvolution and quantification, every lithium-bearing species was closely tracked and four-step soluble lithium polysulfide-mediated lithium sulfur electrochemistry was demonstrated in never before seen detail. Significant irreversiblemore » accumulation of Li 2S is observed on the Li metal anode after four cycles because of sulfur shuttling. We present the application of the method in order to study electrolyte/additive development and lithium protection research can be readily envisaged.« less

Arsenic Speciation of Waters from the Aegean Region, Turkey by Hydride Generation: Atomic Absorption Spectrometry.

PubMed

Çiftçi, Tülin Deniz; Henden, Emur

2016-08-01

Arsenic in drinking water is a serious problem for human health. Since the toxicity of arsenic species As(III) and As(V) is different, it is important to determine the concentrations separately. Therefore, it is necessary to develop an accurate and sensitive method for the speciation of arsenic. It was intended with this work to determine the concentrations of arsenic species in water samples collected from Izmir, Manisa and nearby areas. A batch type hydride generation atomic absorption spectrometer was used. As(V) gave no signal under the optimal measurement conditions of As(III). A certified reference drinking water was analyzed by the method and the results showed excellent agreement with the reported values. The procedure was applied to 34 water samples. Eleven tap water, two spring water, 19 artesian well water and two thermal water samples were analyzed under the optimal conditions.

In Situ NMR Observation of the Temporal Speciation of Lithium Sulfur Batteries during Electrochemical Cycling

DOE PAGES

Wang, Hao; Sa, Niya; He, Meinan; ...

2017-03-03

The understanding of the reaction mechanism and temporal speciation of the lithium sulfur batteries is challenged by complex polysulfide disproportionation chemistry coupled with the precipitation and dissolution of species. In this report, for the first time, we present a comprehensive method to investigate lithium sulfur electrochemistry using in situ 7Li NMR spectroscopy, a technique that is capable of quantitatively capturing the evolution of the soluble and precipitated lithium (poly)sulfides during electrochemical cycling. Furthermore, through deconvolution and quantification, every lithium-bearing species was closely tracked and four-step soluble lithium polysulfide-mediated lithium sulfur electrochemistry was demonstrated in never before seen detail. Significant irreversiblemore » accumulation of Li 2S is observed on the Li metal anode after four cycles because of sulfur shuttling. We present the application of the method in order to study electrolyte/additive development and lithium protection research can be readily envisaged.« less

Carbon dioxide sequestration induced mineral precipitation healing of fractured reservoir seals

NASA Astrophysics Data System (ADS)

Welch, N.; Crawshaw, J.

2017-12-01

Initial experiments and the thermodynaic basis for carbon dioxide sequestration induced mineral precipitation healing of fractures through reservoir seals will be presented. The basis of this work is the potential exists for the dissolution of reservoir host rock formation carbonate minerals in the acidified injection front of CO2 during sequestration or EOR. This enriched brine and the bulk CO2 phase will then flow through the reservoir until contact with the reservoir seal. At this point any fractures present in the reservoir seal will be the preferential flow path for the bulk CO2 phase as well as the acidified brine front. These fractures would currently be filled with non-acidified brine saturated in seal formation brine. When the acidifeid brine from the host formation and the cap rock brine mix there is the potential for minerals to fall out of solution, and for these precipitated minerals to decrease or entirely cut off the fluid flow through the fractures present in a reservoir seal. Initial equilibrium simulations performed using the PHREEQC1 database drived from the PHREEQE2 database are used to show the favorable conditions under which this mineral precipitation can occurs. Bench scale fluid mixing experiments were then performed to determine the kinetics of the mineral precipitation process, and determine the progress of future experiemnts involving fluid flow within fractured anhydrite reservoir seal samples. 1Parkhurst, D.L., and Appelo, C.A.J., 2013, Description of input and examples for PHREEQC version 3—A computer program for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations: U.S. Geological Survey Techniques and Methods, book 6, chap. A43, 497 p., available only at https://pubs.usgs.gov/tm/06/a43/. 2Parkhurst, David L., Donald C. Thorstenson, and L. Niel Plummer. PHREEQE: a computer program for geochemical calculations. No. 80-96. US Geological Survey, Water Resources Division,, 1980.

Sympatric speciation by sexual selection alone is unlikely.

PubMed

Arnegard, Matthew E; Kondrashov, Alexey S

2004-02-01

According to Darwin, sympatric speciation is driven by disruptive, frequency-dependent natural selection caused by competition for diverse resources. Recently, several authors have argued that disruptive sexual selection can also cause sympatric speciation. Here, we use hypergeometric phenotypic and individual-based genotypic models to explore sympatric speciation by sexual selection under a broad range of conditions. If variabilities of preference and display traits are each caused by more than one or two polymorphic loci, sympatric speciation requires rather strong sexual selection when females exert preferences for extreme male phenotypes. Under this kind of mate choice, speciation can occur only if initial distributions of preference and display are close to symmetric. Otherwise, the population rapidly loses variability. Thus, unless allele replacements at very few loci are enough for reproductive isolation, female preferences for extreme male displays are unlikely to drive sympatric speciation. By contrast, similarity-based female preferences that do not cause sexual selection are less destabilizing to the maintenance of genetic variability and may result in sympatric speciation across a broader range of initial conditions. Certain groups of African cichlids have served as the exclusive motivation for the hypothesis of sympatric speciation by sexual selection. Mate choice in these fishes appears to be driven by female preferences for extreme male phenotypes rather than similarity-based preferences, and the evolution of premating reproductive isolation commonly involves at least several genes. Therefore, differences in female preferences and male display in cichlids and other species of sympatric origin are more likely to have evolved as isolating mechanisms under disruptive natural selection.

Mercury(II) and methyl mercury determinations in water and fish samples by using solid phase extraction and cold vapour atomic absorption spectrometry combination.

PubMed

Tuzen, Mustafa; Karaman, Isa; Citak, Demirhan; Soylak, Mustafa

2009-07-01

A method has been developed for mercury(II) and methyl mercury speciation on Staphylococcus aureus loaded Dowex Optipore V-493 micro-column in the presented work, by using cold vapour atomic absorption spectrometry. Selective and sequential elution with 0.1 molL(-1) HCl for methyl mercury and 2 molL(-1) HCl for mercury(II) were performed at the pH range of 2-6. Optimal analytical conditions including pH, amounts of biosorbent, sample volumes were investigated. The detection limits of the analytes were 2.5 ngL(-1) for Hg(II) and 1.7 ngL(-1) for methyl mercury. The capacity of biosorbent for mercury(II) and methyl mercury was 6.5 and 5.4 mgg(-1), respectively. The validation of the presented procedure is performed by the analysis of standard reference material. The speciation procedure established was successfully applied to the speciation of mercury(II) and methyl mercury in natural water and microwave digested fish samples.

A simple and low cost dual-wavelength β-correction spectrophotometric determination and speciation of mercury(II) in water using chromogenic reagent 4-(2-thiazolylazo) resorcinol

NASA Astrophysics Data System (ADS)

Al-Bagawi, A. H.; Ahmad, W.; Saigl, Z. M.; Alwael, H.; Al-Harbi, E. A.; El-Shahawi, M. S.

2017-12-01

The most common problems in spectrophotometric determination of various complex species originate from the background spectral interference. Thus, the present study aimed to overcome the spectral matrix interference for the precise analysis and speciation of mercury(II) in water by dual-wavelength β-correction spectrophotometry using 4-(2-thiazolylazo) resorcinol (TAR) as chromogenic reagent. The principle was based on measuring the correct absorbance for the formed complex of mercury(II) ions with TAR reagent at 547 nm (lambda max). Under optimized conditions, a linear dynamic range of 0.1-2.0 μg mL- 1 with correlation coefficient (R2) of 0.997 were obtained with lower limits of detection (LOD) of 0.024 μg mL- 1 and limit of quantification (LOQ) of 0.081 μg mL- 1. The values of RSD and relative error (RE) obtained for β-correction method and single wavelength spectrophotometry were 1.3, 1.32% and 4.7, 5.9%, respectively. The method was validated in tap and sea water in terms of the data obtained from inductively coupled plasma-optical emission spectrometry (ICP-OES) using student's t and F tests. The developed methodology satisfactorily overcomes the spectral interference in trace determination and speciation of mercury(II) ions in water.

SPECIATED VOC EMISSIONS FROM MODERN GDI LIGHT ...

EPA Pesticide Factsheets

Chassis dynamometer emissions testing was conducted to characterize speciated volatile organic compounds (VOCs), including mobile source air toxics (MSATs) and ozone precursors, in exhaust emissions from three modern gasoline direct injection (GDI) light-duty vehicles. Each GDI vehicle tested in this study utilized slightly different fuel injection technology: Vehicle 1 used a 2.4 liter, naturally aspirated, wall-guided GDI; Vehicle 2 used a 1.8 liter, turbocharged GDI engine; Vehicle 3 used a 1.5 liter, turbocharged, spray-guided GDI engine. Vehicle testing was conducted in a temperature controlled chassis dynamometer test cell at 22 °C over the EPA Federal Test Procedure (FTP) and a portion of the Supplemental FTP (SFTP). The FTP was conducted as a three phase cycle with a cold start, hot transient, and warm start phase (also known as the FTP-75 driving cycle). The SFTP consisted of the US06 driving cycle (conducted without the vehicle’s air conditioning on), which provides a more aggressive driving pattern than the FTP. The vehicles operated on 10 percent ethanol blended gasoline (E10). VOC emissions from diluted vehicle exhaust were sampled over each FTP phase and over the Supplemental FTP with SUMMA canisters for EPA Method TO-15 analysis and with DNPH cartridges for carbonyl analysis by EPA Method TO-11A. This presentation will report the impact of driving cycle and GDI technology on speciated MSAT emissions. MSAT emission rates will be compared

Quantitative analysis of arsenic speciation in guano and ornithogenic sediments using microwave-assisted extraction followed by high-performance liquid chromatography coupled to hydride generation atomic fluorescence spectrometry.

PubMed

Lou, Chuangneng; Liu, Wenqi; Liu, Xiaodong

2014-10-15

Seabird guano is one of the main sources of nutrient fertilizers in remote coastal island areas, but guano-derived contaminants such as arsenic may cause serious threats to local ecosystems and public health issues. In this study, a new method was developed to analyze arsenic speciation in guano and ornithogenic sediments. Good extraction efficiencies of As(III) (arsenite), DMA (dimethylarsinate), MMA (monomethylarsonate) and As(V) (arsenate) were obtained by using 1.0molL(-1) orthophosphoric acid and 0.1molL(-1) ascorbic acid, followed by microwave-assisted extraction and high-performance liquid chromatography coupled to hydride generation atomic fluorescence spectrometry (HPLC-HG-AFS) detection. Under the optimized conditions, the extraction efficiencies of four arsenic species were over 80%. The relative standard deviations (RSDs) were 9.60, 6.15, 6.34 and 2.93% (n=7), and the detection limits (μgL(-1)) were 0.82, 2.38, 1.45 and 2.31 for As(III), DMA, MMA and As(V), respectively. This method was successfully used to determine arsenic speciation in the guano samples collected from the Xisha Islands of the South China Sea, and the results indicated that As(III) and As(V) were the dominant arsenic species in modern and ancient guano, respectively. Copyright © 2014 Elsevier B.V. All rights reserved.

Detecting local diversity-dependence in diversification.

PubMed

Xu, Liang; Etienne, Rampal S

2018-04-06

Whether there are ecological limits to species diversification is a hotly debated topic. Molecular phylogenies show slowdowns in lineage accumulation, suggesting that speciation rates decline with increasing diversity. A maximum-likelihood (ML) method to detect diversity-dependent (DD) diversification from phylogenetic branching times exists, but it assumes that diversity-dependence is a global phenomenon and therefore ignores that the underlying species interactions are mostly local, and not all species in the phylogeny co-occur locally. Here, we explore whether this ML method based on the nonspatial diversity-dependence model can detect local diversity-dependence, by applying it to phylogenies, simulated with a spatial stochastic model of local DD speciation, extinction, and dispersal between two local communities. We find that type I errors (falsely detecting diversity-dependence) are low, and the power to detect diversity-dependence is high when dispersal rates are not too low. Interestingly, when dispersal is high the power to detect diversity-dependence is even higher than in the nonspatial model. Moreover, estimates of intrinsic speciation rate, extinction rate, and ecological limit strongly depend on dispersal rate. We conclude that the nonspatial DD approach can be used to detect diversity-dependence in clades of species that live in not too disconnected areas, but parameter estimates must be interpreted cautiously. © 2018 The Author(s). Evolution published by Wiley Periodicals, Inc. on behalf of The Society for the Study of Evolution.

Nanometer-sized alumina packed microcolumn solid-phase extraction combined with field-amplified sample stacking-capillary electrophoresis for the speciation analysis of inorganic selenium in environmental water samples.

PubMed

Duan, Jiankuan; Hu, Bin; He, Man

2012-10-01

In this paper, a new method of nanometer-sized alumina packed microcolumn SPE combined with field-amplified sample stacking (FASS)-CE-UV detection was developed for the speciation analysis of inorganic selenium in environmental water samples. Self-synthesized nanometer-sized alumina was packed in a microcolumn as the SPE adsorbent to retain Se(IV) and Se(VI) simultaneously at pH 6 and the retained inorganic selenium was eluted by concentrated ammonia. The eluent was used for FASS-CE-UV analysis after NH₃ evaporation. The factors affecting the preconcentration of both Se(IV) and Se(VI) by SPE and FASS were studied and the optimal CE separation conditions for Se(IV) and Se(VI) were obtained. Under the optimal conditions, the LODs of 57 ng L⁻¹ (Se(IV)) and 71 ng L⁻¹ (Se(VI)) were obtained, respectively. The developed method was validated by the analysis of a certified reference material of GBW(E)080395 environmental water and the determined value was in a good agreement with the certified value. It was also successfully applied to the speciation analysis of inorganic selenium in environmental water samples, including Yangtze River water, spring water, and tap water. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemical characterization of organic aerosol above a mid-latitude forest reveals a complex mixture of highly-functionalized chemical species and diverse structural features with temporal variability

NASA Astrophysics Data System (ADS)

Gentner, D. R.; Ditto, J.; Barnes, E.; Khare, P.

2017-12-01

Highly-functionalized organic compounds are known to be a major component of the complex mixture of the particle-phase compounds that comprise organic aerosol, yet little is known about the identity of many of these compounds, and their formation pathways and roles in atmospheric processes are poorly understood. We present results from the comprehensive chemical speciation of PM10 organic aerosols collected in July 2016 at the remote mid-latitude forest field site during PROPHET. Samples were analyzed via liquid and gas chromatography coupled with a quadrupole time-of-flight tandem mass spectrometry (MS×MS) following electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI). 8 hr samples were collected during day- and night-time sampling periods rather than more typical 24-hour samples. This analysis of the organic aerosol yielded over 12,000 unique compounds for which we have high accuracy molecular masses, formulas, and additional information on structural features using MS×MS. O:C ratios were 0.3 on average, yet the top 10% of compounds ranged 0.7-2.3. 70% and 69% of day- and night-time samples were nitrogen-containing, whereas 26% and 24% contained sulfur, respectively. Within these broader molecular categories, we observed a wide variety of molecular features that reveal a diversity of functional groups and moieties. In this presentation, we present the results of our speciation, temporal variability, connections to air parcel back trajectories and other bulk properties, and potential formation pathways.

Evolution of uranium distribution and speciation in mill tailings, COMINAK Mine, Niger.

PubMed

Déjeant, Adrien; Galoisy, Laurence; Roy, Régis; Calas, Georges; Boekhout, Flora; Phrommavanh, Vannapha; Descostes, Michael

2016-03-01

This study investigated the evolution of uranium distribution and speciation in mill tailings from the COMINAK mine (Niger), in production since 1978. A multi-scale approach was used, which combined high resolution remote sensing imagery, ICP-MS bulk rock analyses, powder X-ray diffraction, Scanning Electron Microscopy, Focused Ion Beam--Transmission Electron Microscopy and X-ray Absorption Near Edge Spectroscopy. Mineralogical analyses showed that some ore minerals, including residual uraninite and coffinite, undergo alteration and dissolution during tailings storage. The migration of uranium and other contaminants depends on (i) the chemical stability of secondary phases and sorbed species (dissolution and desorption processes), and (ii) the mechanical transport of fine particles bearing these elements. Uranium is stabilized after formation of secondary uranyl sulfates and phosphates, and adsorbed complexes on mineral surfaces (e.g. clay minerals). In particular, the stock of insoluble uranyl phosphates increases with time, thus contributing to the long-term stabilization of uranium. At the surface, a sulfate-cemented duricrust is formed after evaporation of pore water. This duricrust limits water infiltration and dust aerial dispersion, though it is enriched in uranium and many other elements, because of pore water rising from underlying levels by capillary action. Satellite images provided a detailed description of the tailings pile over time and allow monitoring of the chronology of successive tailings deposits. Satellite images suggest that uranium anomalies that occur at deep levels in the pile are most likely former surface duricrusts that have been buried under more recent tailings. Copyright © 2015 Elsevier B.V. All rights reserved.

Intercomparison of analytical methods for arsenic speciation in human urine.

PubMed

Crecelius, E; Yager, J

1997-06-01

An intercomparison exercise was conducted for the quantification of arsenic species in spiked human urine. The primary objective of the exercise was to determine the variance among laboratories in the analysis of arsenic species such as inorganic As (As+3 and As+5), monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA). Laboratories that participated had previous experience with arsenic speciation analysis. The results of this interlaboratory comparison are encouraging. There is relatively good agreement on the concentrations of these arsenic species in urine at concentrations that are relevant to research on the metabolism of arsenic in humans and other mammals. Both the accuracy and precision are relatively poor for arsenic concentrations of less than about 5 micrograms/l.

Speciation in Drosophila: from phenotypes to molecules.

PubMed

Orr, H Allen; Masly, J P; Phadnis, Nitin

2007-01-01

Study of the genetics of speciation--and especially of the genetics of intrinsic postzygotic isolation-has enjoyed remarkable progress over the last 2 decades. Indeed progress has been so rapid that one might be tempted to ask if the genetics of postzygotic isolation is now wrapped up. Here we argue that the genetics of speciation is far from complete. In particular, we review 2 topics where recent work has revealed major surprises: 1) the role of meiotic drive in hybrid sterility and 2) the role of gene transposition in speciation. These surprises, and others like them, suggest that evolutionary biologists may understand less about the genetic basis of speciation than seemed likely a few years ago.

Fast and robust standard-deviation-based method for bulk motion compensation in phase-based functional OCT.

PubMed

Wei, Xiang; Camino, Acner; Pi, Shaohua; Cepurna, William; Huang, David; Morrison, John C; Jia, Yali

2018-05-01

Phase-based optical coherence tomography (OCT), such as OCT angiography (OCTA) and Doppler OCT, is sensitive to the confounding phase shift introduced by subject bulk motion. Traditional bulk motion compensation methods are limited by their accuracy and computing cost-effectiveness. In this Letter, to the best of our knowledge, we present a novel bulk motion compensation method for phase-based functional OCT. Bulk motion associated phase shift can be directly derived by solving its equation using a standard deviation of phase-based OCTA and Doppler OCT flow signals. This method was evaluated on rodent retinal images acquired by a prototype visible light OCT and human retinal images acquired by a commercial system. The image quality and computational speed were significantly improved, compared to two conventional phase compensation methods.

Simultaneous speciation of inorganic arsenic, selenium and tellurium in environmental water samples by dispersive liquid liquid microextraction combined with electrothermal vaporization inductively coupled plasma mass spectrometry.

PubMed

Liu, Ying; He, Man; Chen, Beibei; Hu, Bin

2015-09-01

A new method based on dispersive liquid liquid microextraction (DLLME) combined with electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) was developed for the simultaneous speciation of inorganic arsenic (As), selenium (Se) and tellurium (Te) with sodium diethyldithiocarbamate (DDTC) as both chelating reagent and chemical modifier. As(III), Se(IV) and Te(IV) were transformed into DDTC-chelates at pH 7 and extracted into the fine droplets formed by injecting the binary solution of bromobenzene (extraction solvent) and methanol (dispersive solvent) into the sample solution. After phase separation by centrifugation, As(III), Se(IV) and Te(IV) preconcentrated in the organic phase were determined by ETV-ICP-MS. Total inorganic As, Se and Te were obtained by reducing As(V), Se(VI) and Te(VI) to As(III), Se(IV) and Te(IV) with L-cysteine, which were then subjected to the same DLLME-ETV-ICP-MS process. The concentration of As(V), Se(VI), Te(VI) were calculated by subtracting the concentration of As(III), Se(IV) and Te(IV) from the total inorganic As, Se and Te, respectively. The main factors affecting the microextraction efficiency and the vaporization behavior of target species were investigated in detail. Under the optimal conditions, the limits of detection were 2.5, 8.6 and 0.56 ng L(-1) for As(III), Se(IV) and Te(IV), respectively, with the relative standard deviations (n=7) of 8.5-9.7%. The developed method was applied to the speciation of inorganic As, Se and Te in Certified Reference Materials of GSBZ50004-88, GBW(E)080395 and GBW(E)080548 environmental waters, and the determined values are in good agreement with the certified values. The method was also successfully applied to the simultaneous speciation of inorganic As, Se and Te in different environmental water samples with the recoveries in the range of 86.3-107% for the spiked samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Testing comparative phylogeographic models of marine vicariance and dispersal using a hierarchical Bayesian approach

PubMed Central

2008-01-01

Background Marine allopatric speciation is an enigma because pelagic larval dispersal can potentially connect disjunct populations thereby preventing reproductive and morphological divergence. Here we present a new hierarchical approximate Bayesian computation model (HABC) that tests two hypotheses of marine allopatric speciation: 1.) "soft vicariance", where a speciation involves fragmentation of a large widespread ancestral species range that was previously connected by long distance gene flow; and 2.) peripatric colonization, where speciations in peripheral archipelagos emerge from sweepstakes colonizations from central source regions. The HABC approach analyzes all the phylogeographic datasets at once in order to make across taxon-pair inferences about biogeographic processes while explicitly allowing for uncertainty in the demographic differences within each taxon-pair. Our method uses comparative phylogeographic data that consists of single locus mtDNA sequences from multiple co-distributed taxa containing pairs of central and peripheral populations. We use the method on two comparative phylogeographic data sets consisting of cowrie gastropod endemics co-distributed in the Hawaiian (11 taxon-pairs) and Marquesan archipelagos (7 taxon-pairs). Results Given the Marquesan data, we find strong evidence of simultaneous colonization across all seven cowrie gastropod endemics co-distributed in the Marquesas. In contrast, the lower sample sizes in the Hawaiian data lead to greater uncertainty associated with the Hawaiian estimates. Although, the hyper-parameter estimates point to soft vicariance in a subset of the 11 Hawaiian taxon-pairs, the hyper-prior and hyper-posterior are too similar to make a definitive conclusion. Both results are not inconsistent with what is known about the geologic history of the archipelagos. Simulations verify that our method can successfully distinguish these two histories across a wide range of conditions given sufficient sampling. Conclusion Although soft vicariance and colonization are likely to produce similar genetic patterns when a single taxon-pair is used, our hierarchical Bayesian model can potentially detect if either history is a dominant process across co-distributed taxon-pairs. As comparative phylogeographic datasets grow to include > 100 co-distributed taxon-pairs, the HABC approach will be well suited to dissect temporal patterns in community assembly and evolution, thereby providing a bridge linking comparative phylogeography with community ecology. PMID:19038027

Knowledge gained from analyzing mercury speciation data monitored in North America

NASA Astrophysics Data System (ADS)

Zhang, L.; Cheng, I.; Gay, D. A.; Xu, X.; Wu, Z.

2017-12-01

This presentation summarizes knowledge gained in several recent studies through analysis and application of mercury (Hg) speciation data monitored in North America. Annual Hg dry deposition to vegetated surfaces in the rural or remote environment in North America was dominated by leaf uptake of gaseous elemental mercury (GEM), contrary to what was commonly assumed in earlier studies which frequently omitted GEM dry deposition as an important process (Zhang et al., EST, 2016). Dry deposition exceeded wet deposition by a large margin in all of the seasons except in the summer at the majority of the sites. Based on the gaseous oxidized mercury (GOM) concentrations predicted from measured Hg wet deposition using a scavenging ratio method, multi-year average GOM concentrations collected using Tekran speciation instrument were likely biased low by a factor of 2 at about half of the studied sites (Cheng and Zhang, EST, 2017). A decline in the number of source regions impacting ambient GEM and GOM was found from 2005-2014 at an eastern U.S. site through concentration-weighted trajectory (CWT) analysis (Cheng et al., JAS, 2017). Source contributions decreased by up to 20% for GEM, greater than 60% for GOM, and 20-60% for PBM in 2011-2014 than in 2006-2008, largely due to power plant Hg emission reductions since 2009. A study comparing Positive Matrix Factorization (PMF) and Principal Components Analysis (PCA) receptor methods identified similar sources impacting Kejimkujik National Park, Canada, including combustion, industrial sulfur, photochemistry and re-emissions, and oceanic sea-salt emissions. Improving the quality of the Hg data used in receptor methods by imputation did not improve the PMF results, but reducing the fraction of below detection limit data was effective (Xu et al., ACP, 2017). PCA results using reactive mercury (RM=GOM+PBM) or excluding low GOM values were similar to those using the original data. Source contributions from CWT analysis were more sensitive to the use of RM than excluding low GOM values (Cheng et al., ACP, 2016). Future research needs are recommended for improving the understanding of speciated atmospheric mercury based on a series of recently published review papers (Zhang et al., ACP, 2017).

Variation of the NMVOC speciation in the solvent sector and the sensitivity of modelled tropospheric ozone

NASA Astrophysics Data System (ADS)

von Schneidemesser, E.; Coates, J.; Denier van der Gon, H. A. C.; Visschedijk, A. J. H.; Butler, T. M.

2016-06-01

Non-methane volatile organic compounds (NMVOCs) are detrimental to human health owing to the toxicity of many of the NMVOC species, as well as their role in the formation of secondary air pollutants such as tropospheric ozone (O3) and secondary organic aerosol. The speciation and amount of NMVOCs emitted into the troposphere are represented in emission inventories (EIs) for input to chemical transport models that predict air pollutant levels. Much of the information in EIs pertaining to speciation of NMVOCs is likely outdated, but before taking on the task of providing an up-to-date and highly speciated EI, a better understanding of the sensitivity of models to the change in NMVOC input would be highly beneficial. According to the EIs, the solvent sector is the most important sector for NMVOC emissions. Here, the sensitivity of modelled tropospheric O3 to NMVOC emission inventory speciation was investigated by comparing the maximum potential difference in O3 produced using a variety of reported solvent sector EI speciations in an idealized study using a box model. The sensitivity was tested using three chemical mechanisms that describe O3 production chemistry, typically employed for different types of modelling scales - point (MCM v3.2), regional (RADM2), and global (MOZART-4). In the box model simulations, a maximum difference of 15 ppbv (ca. 22% of the mean O3 mixing ratio of 69 ppbv) between the different EI speciations of the solvent sector was calculated. In comparison, for the same EI speciation, but comparing the three different mechanisms, a maximum difference of 6.7 ppbv was observed. Relationships were found between the relative contribution of NMVOC compound classes (alkanes and oxygenated species) in the speciations to the amount of Ox produced in the box model. These results indicate that modelled tropospheric O3 is sensitive to the speciation of NMVOCs as specified by emission inventories, suggesting that detailed updates to the EI speciation information would be warranted. Furthermore, modelled tropospheric O3 was also sensitive to the choice of chemical mechanism and further evaluation of both of these sensitivities in more realistic chemical-transport models is needed.

Magnetic effervescent tablet-assisted ionic liquid dispersive liquid-liquid microextraction of selenium for speciation in foods and beverages.

PubMed

Wang, Xiaojun; Wu, Long; Cao, Jiaqi; Hong, Xincheng; Ye, Rui; Chen, Weiji; Yuan, Ting

2016-07-01

A novel, simple and rapid method based on magnetic effervescent tablet-assisted ionic liquid dispersive liquid-liquid microextraction (MEA-IL-DLLME) followed by graphite furnace atomic absorption spectrometry (GFAAS) determination was established for the speciation of selenium in various food and beverage samples. In the procedure, a special magnetic effervescent tablet containing CO2 sources (sodium carbonate and sodium dihydrogenphosphate), ionic liquids and Fe3O4 magnetic nanoparticles (MNPs) was used to combine extractant dispersion and magnetic recovery procedures into a single step. The parameters influencing the microextraction efficiency, such as pH of the sample solution, volume of ionic liquid, amount of MNPs, concentration of the chelating agent, salt effect and matrix effect were investigated and optimised. Under the optimised conditions, the limits of detection (LODs) for Se(IV) were 0.021 μg l(-)(1) and the linear dynamic range was 0.05-5.0 μg l(-)(1). The relative standard deviation for seven replicate measurements of 1.0 μg l(-)(1) of Se(IV) was 2.9%. The accuracy of the developed method was evaluated by analysis of the standard reference materials (GBW10016 tea, GBW10017 milk powder, GBW10043 Liaoning rice, GBW10046 Henan wheat, GBW10048 celery). The proposed method was successfully applied to food and beverage samples including black tea, milk powder, mushroom, soybean, bamboo shoots, energy drink, bottled water, carbonated drink and mineral water for the speciation of Se(IV) and Se(VI) with satisfactory relative recoveries (92.0-108.1%).

Processes of zinc attenuation by biogenic manganese oxides forming in the hyporheic zone of Pinal Creek, Arizona

PubMed Central

Fuller, Christopher C.; Bargar, John R.

2014-01-01

The distribution and speciation of Zn sorbed to biogenic Mn oxides forming in the hyporheic zone of Pinal Creek, AZ, was investigated using micro-focused Extended X-ray Absorption Fine Structure (EXAFS) and X-ray fluorescence (μSXRF) mapping , bulk EXAFS, and chemical extraction. μSXRF and chemical extractions show that contaminant Zn co-varied with Mn in streambed sediment grain coatings. Bulk and micro-focused EXAFS spectra of Zn in the biogenic Mn oxides coating are indicative of Zn forming triple corner sharing inner-sphere complexes over octahedral vacancies in the Mn oxide sheet structure. Zn desorbed in response to decreasing in pH in batch experiments and resulted in near-equal dissolved Zn at each pH over a 10-fold range in solid to solution ratio. The geometry of sorbed Zn was unchanged after 50% desorption at pH 5, indicating desorption is not controlled by dissolution of secondary Zn phases. In sum, these findings support the idea that Zn attenuation in Pinal Creek is largely controlled by sorption to microbial Mn oxides forming in the streambed during hyporheic exchange. Sorption to biogenic Mn oxides is likely an important process in Zn attenuation in circum-neutral pH reaches of many acid-mine drainage contaminated streams when dissolved Mn is present. PMID:24460038

Colloidal complexed silver and silver nanoparticles in extrapallial fluid of Mytilus edulis.

PubMed

Zuykov, Michael; Pelletier, Emilien; Demers, Serge

2011-02-01

Metal transport in mollusk extrapallial fluid (EPF) that acts as a "bridge" between soft tissues and shell has surprisingly received little attention until now. Using ultrafiltration and radiotracer techniques we determined silver concentrations and speciation in the EPF of the blue mussel Mytilus edulis after short-term uptake and depuration laboratory experiments. Radiolabelled silver ((¹¹⁰m)Ag) was used in dissolved or nanoparticulate phases (AgNPs < 40 nm), with a similar low Ag concentration (total radioactive and cold Ag ~0.7 μg/L) in a way that mussels could uptake radiotracers only from seawater. Our results indicated that silver nanoparticles were transported to the EPF of blue mussels at a level similar to the Ag ionic form. Bulk activity of radiolabelled silver in the EPF represented only up to 7% of the bulk activity measured in the whole mussels. The EPF extracted from mussels exposed to both treatments exhibited an Ag colloidal complexed form based on EPF ultrafiltration through a 3 kDa filter. This original study brings new insights to internal circulation of nanoparticles in living organisms and contributes to the international effort in studying the potential impacts of engineered nanomaterials on marine bivalves which play an essential role in coastal ecosystems, and are important contributors to human food supply from the sea. © 2010 Elsevier Ltd. All rights reserved.

Surface speciation and interactions between adsorbed chloride and water on cerium dioxide

NASA Astrophysics Data System (ADS)

Sutherland-Harper, Sophie; Taylor, Robin; Hobbs, Jeff; Pimblott, Simon; Pattrick, Richard; Sarsfield, Mark; Denecke, Melissa; Livens, Francis; Kaltsoyannis, Nikolas; Arey, Bruce; Kovarik, Libor; Engelhard, Mark; Waters, John; Pearce, Carolyn

2018-06-01

Ceria particles with different specific surface areas (SSA) were contaminated with chloride and water, then heat treated at 500 and 900 °C to investigate sorption behaviour of these species on metal oxides. Results from x-ray photoelectron spectroscopy and infrared spectroscopy showed chloride and water adsorption onto particles increased with surface area and that these species were mostly removed on heat treatment (from 6.3 to 0.8 at% Cl- on high SSA and from 1.4 to 0.4 at% on low SSA particles). X-ray diffraction revealed that chloride was not incorporated into the bulk ceria structure, but crystal size increased upon contamination. Ce LIII-edge x-ray absorption spectroscopy confirmed that chloride was not present in the first co-ordination sphere around Ce(IV) ions, so was not bonded to Ce as chloride in the bulk structure. Sintering of contaminated high SSA particles occurred with heat treatment at 900 °C, and they resembled low SSA particles synthesised at this temperature. Physical chloride-particle interactions were investigated using electron microscopy and energy dispersive x-ray analysis, showing that chloride was homogeneously distributed on ceria and that reduction of porosity did not trap surface-sorbed chloride inside the particles as surface area was reduced during sintering. This has implications for stabilisation of chloride-contaminated PuO2 for long term storage.

Combustible and incombustible speciation of Cl and S in various components of municipal solid waste.

PubMed

Watanabe, Nobuhisa; Yamamoto, Osamu; Sakai, Mamoru; Fukuyama, Johji

2004-01-01

Chlorine (Cl) and sulfur (S) in municipal solid waste (MSW) are important reactive elements during combustion. They generate the acidic pollutants HCl and SOx, and, furthermore, produce and suppress organic chlorinated compounds. Nevertheless, few practical reports about Cl and S content in MSW have been published. In combustion and recycling processes, both combustible Cl and S, and incombustible Cl and S species are equally important. This paper presents the results of a comprehensive study about combustible and incombustible Cl and S in MSW components, including kitchen garbage, paper, textiles, wood and leaves, plastics and small chips. By integrating this collected data with data about MSW composition, not only the overall content of Cl and S in MSW, but also the origins of both combustible and incombustible Cl and S were estimated. The average Cl content in bulk MSW was 3.7 g/kg of raw MSW, of which 2.7 and 1.0 g/kg were combustible and incombustible, respectively. The Cl contribution from plastics was 76% and 27% with respect to combustible and incombustible states. The average S content in bulk MSW was 0.81 g/kg of raw MSW, of which 0.46 g/kg was combustible and 0.35 g/kg was incombustible. Combustible S was mainly due to synthetic textiles, while incombustible S was primarily from paper.

Bright metal coatings from sustainable electrolytes: the effect of molecular additives on electrodeposition of nickel from a deep eutectic solvent.

PubMed

Abbott, Andrew P; Ballantyne, Andrew; Harris, Robert C; Juma, Jamil A; Ryder, Karl S

2017-01-25

Organic and inorganic additives are often added to nickel electroplating solutions to improve surface finish, reduce roughness and promote uniform surface morphology of the coatings. Such additives are usually small molecules and often referred to as brighteners or levellers. However, there have been limited investigations into the effect of such additives on electrodeposition from ionic liquids (ILs) and deep eutectic solvents (DESs). Here we study the effect of four additives on electrolytic nickel plating from an ethyleneglycol based DES; these are nicotinic acid (NA), methylnicotinate (MN), 5,5-dimethylhydantoin (DMH) and boric acid (BA). The additives show limited influence on the bulk Ni(ii) speciation but have significant influence on the electrochemical behaviour of Ni deposition. Small concentrations (ca. 15 mM) of NA and MN show inhibition of Ni(ii) reduction whereas high concentrations of DMH and BA are required for a modest difference in behaviour from the additive free system. NA and MN also show that they significantly alter the nucleation and growth mechanism when compared to the additive free system and those with DMH and BA. Each of the additive systems had the effect of producing brighter and flatter bulk electrodeposits with increased coating hardness but XRD shows that NA and MN direct crystal growth to the [111] orientation whereas DMH and BA direct crystal growth to the [220] orientation.

How humans drive speciation as well as extinction

PubMed Central

Maron, M.

2016-01-01

A central topic for conservation science is evaluating how human activities influence global species diversity. Humanity exacerbates extinction rates. But by what mechanisms does humanity drive the emergence of new species? We review human-mediated speciation, compare speciation and known extinctions, and discuss the challenges of using net species diversity as a conservation objective. Humans drive rapid evolution through relocation, domestication, hunting and novel ecosystem creation—and emerging technologies could eventually provide additional mechanisms. The number of species relocated, domesticated and hunted during the Holocene is of comparable magnitude to the number of observed extinctions. While instances of human-mediated speciation are known, the overall effect these mechanisms have upon speciation rates has not yet been quantified. We also explore the importance of anthropogenic influence upon divergence in microorganisms. Even if human activities resulted in no net loss of species diversity by balancing speciation and extinction rates, this would probably be deemed unacceptable. We discuss why, based upon ‘no net loss’ conservation literature—considering phylogenetic diversity and other metrics, risk aversion, taboo trade-offs and spatial heterogeneity. We conclude that evaluating speciation alongside extinction could result in more nuanced understanding of biosphere trends, clarifying what it is we actually value about biodiversity. PMID:27358365

Interaction between Digestive Strategy and Niche Specialization Predicts Speciation Rates across Herbivorous Mammals.

PubMed

Tran, Lucy A P

2016-04-01

Biotic and abiotic factors often are treated as mutually exclusive drivers of diversification processes. In this framework, ecological specialists are expected to have higher speciation rates than generalists if abiotic factors are the primary controls on species diversity but lower rates if biotic interactions are more important. Speciation rate is therefore predicted to positively correlate with ecological specialization in the purely abiotic model but negatively correlate in the biotic model. In this study, I show that the positive relationship between ecological specialization and speciation expected from the purely abiotic model is recovered only when a species-specific trait, digestive strategy, is modeled in the terrestrial, herbivorous mammals (Mammalia). This result suggests a more nuanced model in which the response of specialized lineages to abiotic factors is dependent on a biological trait. I also demonstrate that the effect of digestive strategy on the ecological specialization-speciation rate relationship is not due to a difference in either the degree of ecological specialization or the speciation rate between foregut- and hindgut-fermenting mammals. Together, these findings suggest that a biological trait, alongside historical abiotic events, played an important role in shaping mammal speciation at long temporal and large geographic scales.

How humans drive speciation as well as extinction.

PubMed

Bull, J W; Maron, M

2016-06-29

A central topic for conservation science is evaluating how human activities influence global species diversity. Humanity exacerbates extinction rates. But by what mechanisms does humanity drive the emergence of new species? We review human-mediated speciation, compare speciation and known extinctions, and discuss the challenges of using net species diversity as a conservation objective. Humans drive rapid evolution through relocation, domestication, hunting and novel ecosystem creation-and emerging technologies could eventually provide additional mechanisms. The number of species relocated, domesticated and hunted during the Holocene is of comparable magnitude to the number of observed extinctions. While instances of human-mediated speciation are known, the overall effect these mechanisms have upon speciation rates has not yet been quantified. We also explore the importance of anthropogenic influence upon divergence in microorganisms. Even if human activities resulted in no net loss of species diversity by balancing speciation and extinction rates, this would probably be deemed unacceptable. We discuss why, based upon 'no net loss' conservation literature-considering phylogenetic diversity and other metrics, risk aversion, taboo trade-offs and spatial heterogeneity. We conclude that evaluating speciation alongside extinction could result in more nuanced understanding of biosphere trends, clarifying what it is we actually value about biodiversity. © 2016 The Author(s).

Optimizing Standard Sequential Extraction Protocol With Lake And Ocean Sediments

EPA Science Inventory

The environmental mobility/availability behavior of radionuclides in soils and sediments depends on their speciation. Experiments have been carried out to develop a simple but robust radionuclide sequential extraction method for identification of radionuclide partitioning in sed...

Biomic specialization and speciation rates in ruminants (Cetartiodactyla, Mammalia): a test of the resource-use hypothesis at the global scale.

PubMed

Cantalapiedra, Juan L; Hernández Fernández, Manuel; Morales, Jorge

2011-01-01

The resource-use hypothesis proposed by E.S. Vrba predicts that specialist species have higher speciation and extinction rates than generalists because they are more susceptible to environmental changes and vicariance. In this work, we test some of the predictions derived from this hypothesis on the 197 extant and recently extinct species of Ruminantia (Cetartiodactyla, Mammalia) using the biomic specialization index (BSI) of each species, which is based on its distribution within different biomes. We ran 10000 Monte Carlo simulations of our data in order to get a null distribution of BSI values against which to contrast the observed data. Additionally, we drew on a supertree of the ruminants and a phylogenetic likelihood-based method (QuaSSE) for testing whether the degree of biomic specialization affects speciation rates in ruminant lineages. Our results are consistent with the predictions of the resource-use hypothesis, which foretells a higher speciation rate of lineages restricted to a single biome (BSI = 1) and higher frequency of specialist species in biomes that underwent high degree of contraction and fragmentation during climatic cycles. Bovids and deer present differential specialization across biomes; cervids show higher specialization in biomes with a marked hydric seasonality (tropical deciduous woodlands and schlerophyllous woodlands), while bovids present higher specialization in a greater variety of biomes. This might be the result of divergent physiological constraints as well as a different biogeographic and evolutionary history.

Biomic Specialization and Speciation Rates in Ruminants (Cetartiodactyla, Mammalia): A Test of the Resource-Use Hypothesis at the Global Scale

PubMed Central

Cantalapiedra, Juan L.; Hernández Fernández, Manuel; Morales, Jorge

2011-01-01

The resource-use hypothesis proposed by E.S. Vrba predicts that specialist species have higher speciation and extinction rates than generalists because they are more susceptible to environmental changes and vicariance. In this work, we test some of the predictions derived from this hypothesis on the 197 extant and recently extinct species of Ruminantia (Cetartiodactyla, Mammalia) using the biomic specialization index (BSI) of each species, which is based on its distribution within different biomes. We ran 10000 Monte Carlo simulations of our data in order to get a null distribution of BSI values against which to contrast the observed data. Additionally, we drew on a supertree of the ruminants and a phylogenetic likelihood-based method (QuaSSE) for testing whether the degree of biomic specialization affects speciation rates in ruminant lineages. Our results are consistent with the predictions of the resource-use hypothesis, which foretells a higher speciation rate of lineages restricted to a single biome (BSI = 1) and higher frequency of specialist species in biomes that underwent high degree of contraction and fragmentation during climatic cycles. Bovids and deer present differential specialization across biomes; cervids show higher specialization in biomes with a marked hydric seasonality (tropical deciduous woodlands and schlerophyllous woodlands), while bovids present higher specialization in a greater variety of biomes. This might be the result of divergent physiological constraints as well as a different biogeographic and evolutionary history. PMID:22174888

A world-wide perspective on crucifer speciation and evolution: phylogenetics, biogeography and trait evolution in tribe Arabideae

PubMed Central

Karl, Robert; Koch, Marcus A.

2013-01-01

Background and Aims Tribe Arabideae are the most species-rich monophyletic lineage in Brassicaceae. More than 500 species are distributed in the majority of mountain and alpine regions worldwide. This study provides the first comprehensive phylogenetic analysis for the species assemblage and tests for association of trait and characters, providing the first explanations for the enormous species radiation since the mid Miocene. Methods Phylogenetic analyses of DNA sequence variation of nuclear encoded loci and plastid DNA are used to unravel a reliable phylogenetic tree. Trait and ancestral area reconstructions were performed and lineage-specific diversification rates were calculated to explain various radiations in the last 15 Myr in space and time. Key Results A well-resolved phylogenetic tree demonstrates the paraphyly of the genus Arabis and a new systematic concept is established. Initially, multiple radiations involved a split between lowland annuals and mountain/alpine perennial sister species. Subsequently, increased speciation rates occur in the perennial lineages. The centre of origin of tribe Arabideae is most likely the Irano-Turanian region from which the various clades colonized the temperate mountain and alpine regions of the world. Conclusions Mid Miocene early diversification started with increased speciation rates due to the emergence of various annual lineages. Subsequent radiations were mostly driven by diversification within perennial species during the Pliocene, but increased speciation rates also occurred during that epoch. Taxonomic concepts in Arabis are still in need of a major taxonomic revision to define monophyletic groups. PMID:23904444

Towards a global historical biogeography of Palms

NASA Astrophysics Data System (ADS)

Couvreur, Thomas; Baker, William J.; Frigerio, Jean-Marc; Sepulchre, Pierre; Franc, Alain

2017-04-01

Four mechanisms are at work for deciphering historical biogeography of plants : speciation, extinction, migration, and drift (a sort of neutral speciation). The first three mechanisms are under selection pressure of the environment, mainly the climate and connectivity of land masses. Hence, an accurate history of climate and connectivity or non connectivity between landmasses, as well as orogenesis processes, can shed new light on the most likely speciation events and migration routes driven by paleogeography and paleoclimatology. Currently, some models exist (like DIVA) to infer the most parsimonious history (in the number of migration events) knowing the speciation history given by phylogenies (extinction are mostly unknown), in a given setting of climate and landmass connectivity. In a previous project, we have built in collaboration with LSCE a series of paleogeographic and paleoclimatic maps since the Early Cretaceous. We have developed a program, called Aran, which enables to extend DIVA to a time series of varying paleoclimatic and paleogeogarphic conditions. We apply these new methods and data to unravel the biogeographic history of palms (Arecaceae), a pantropical family of 182 genera and >2600 species whose divergence is dated in Late Cretaceous (100 My). Based on a robust dated molecular phylogeny, novel paleoclimatic and paleogeographic maps, we will generate an updated biogeographic history of Arecaceae inferred from the most parsimonious history using Aran. We will discuss the results, and put them in context with what is known and needed to provide a global biogeographic history of tropical palms.

The (biological) speciation of vanadate(V) as revealed by (51)V NMR: A tribute on Lage Pettersson and his work.

PubMed

Rehder, Dieter

2015-06-01

Four decades of research carried out by Lage Pettersson, his group and his coworkers are reviewed, research that has been directed predominantly towards the speciation of vanadate and systems containing, along with vanadate and co-reactants such as phosphate and peroxide, biologically relevant organics. In particular, those organics have been addressed that either are (potential) ligands for vanadate-derived coordination compounds generated at physiological conditions and/or function as constituents in medicinally interesting oxidovanadium compounds. Examples for molecules introduced in the context of the physiological vanadate-ligand interaction include the dipeptides Pro-Ala, Ala-Gly, Ala-His and Ala-Ser, the serum constituents lactate and citrate, and the nucleobases adenosine and uridine. The speciation in the vanadate-picolinate and vanadate-maltol systems is geared towards insulin-enhancing vanadium drugs. The speciation as a function of pH, ionic strength and the concentration of vanadate and the ligand(s) is based on potentiometric and (51)V NMR investigations, a methodical combination that allows reliable access to composition, formation constants and, to some extent, also structural details for the manifold of species present in aqueous media at physiological pH and beyond. The time frame 1971 to 2014 is reviewed, emphasizing the interval 1985 to 2006, and thus focusing on biologically interesting vanadium systems. Figurative representations from the original literature have been included. Copyright © 2015 Elsevier Inc. All rights reserved.

Speciation in fungal and oomycete plant pathogens

USDA-ARS?s Scientific Manuscript database

The process of speciation by definition involves evolution of one or more reproductive isolating mechanisms that split a single species into two that can no longer interbreed. Determination of which processes are responsible for speciation is important yet challenging. Several studies have proposed ...

A STUDY OF GAS-PHASE MERCURY SPECIATION USING DETAILED CHEMICAL KINETICS

EPA Science Inventory

Mercury (Hg) speciation in combustion-generated flue gas is modeled using a detailed chemical mechanism consisting of 60 reactions and 21 species. This speciation model accounts for chlorination and oxidation of key flue-gas components, including elemental mercury. Results indica...

Ruminant-specific multiple duplication events of PRDM9 before speciation

USDA-ARS?s Scientific Manuscript database

Understanding the genetic and evolutionary mechanisms of speciation genes in sexually reproducing organisms would provide important insights into mammalian reproduction and fitness. PRDM9, a widely known speciation gene, has recently gained attention for its important role in meiotic recombination a...

The Development and Uses of EPA's SPECIATE Database

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency's (EPA) repository of volatile organic compounds (VOC) and particulate matter (PM) speciation profiles of air pollution sources. These source profiles can be used to (l) provide input to chemical mass balance (CMB) receptor mod...

Novel separation method for highly sensitive speciation of cancerostatic platinum compounds by HPLC-ICP-MS.

PubMed

Hann, S; Stefánka, Zs; Lenz, K; Stingeder, G

2005-01-01

A high-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) method is presented for analysis of cisplatin, monoaquacisplatin, diaquacisplatin, carboplatin, and oxaliplatin in biological and environmental samples. Chromatographic separation was achieved on pentafluorophenylpropyl-functionalized silica gel. For cisplatin, carboplatin, and oxaliplatin limits of detection of 0.09, 0.10, and 0.15 microg L(-1), respectively, were calculated at m/z 194, using aqueous standard solutions. (3 microL injection volume). The method was utilized for model experiments studying the stability of carboplatin and oxaliplatin at different chloride concentrations simulating wastewater and surface water conditions. It was found that a high fraction of carboplatin is stable in ultrapure water and in solutions containing 1.5 mol L(-1) Cl-, whereas oxaliplatin degradation was increased by increasing the chloride concentration. In order to support the assessment of oxaliplatin eco-toxicology, the method was tested for speciation of patient urine. The urine sample contained more than 17 different reaction products, which demonstrates the extensive biotransformation of the compound. In a second step of the study the method was successfully evaluated for monitoring cancerostatic platinum compounds in hospital waste water.

Evaluation of extraction methods for hexavalent chromium determination in dusts, ashes, and soils

USGS Publications Warehouse

Wolf, Ruth E.; Wilson, Stephen A.

2010-01-01

One of the difficulties in performing speciation analyses on solid samples is finding a suitable extraction method. Traditional methods for extraction of hexavalent chromium, Cr(VI), in soils, such as SW846 Method 3060A, can be tedious and are not always compatible with some determination methods. For example, the phosphate and high levels of carbonate and magnesium present in the U.S. Environmental Protection Agency (USEPA) Method 3060A digestion for Cr(VI) were found to be incompatible with the High Performance Liquid Chromatography-Inductively Coupled Plasma-Mass Spectrometry (HPLC-ICP-MS) detection method used by our laboratory. Modification of Method 3060A by eliminating the use of the phosphate buffer provided improved performance with the detection method, however dilutions are still necessary to achieve good chromatographic separation and detection of Cr(VI). An ultrasonic extraction method using a 1 mM Na2CO3 - 9 mM NaHCO3 buffer solution, adapted from Occupational Safety and Health Administration (OSHA) Method ID215, has been used with good results for the determination of Cr(VI) in air filters. The average recovery obtained for BCR-545 - Welding Dust Loaded on Filter (IRMM, Belgium) using this method was 99 percent (1.2 percent relative standard deviation) with no conversion of Cr(VI) to Cr(III) during the extraction process. This ultrasonic method has the potential for use with other sample matrices, such as ashes and soils. Preliminary investigations using NIST 2701 (Hexavalent Chromium in Contaminated Soil) loaded onto quartz filters showed promising results with approximately 90 percent recovery of the certified Cr(VI) value. Additional testing has been done using NIST 2701 and NIST 2700 using different presentation methods. Extraction efficiency of bulk presentation, where small portions of the sample are added to the bottom of the extraction vessel, will be compared with supported presentation, where small portions of the sample are loaded onto a quartz filter prior to extraction. In addition, results obtained from the standard grinding preparation of NIST 2701 and NIST 2700 will be compared with micronizing to reduce particle size before extraction.

EPA’s SPECIATE 4.4 Database - Development and Uses

EPA Science Inventory

SPECIATE is the EPA's repository of TOG, PM, and Other Gases speciation profiles of air pollution sources. It includes weight fractions of both organic species and PM and provides data in consistent units. Species include metals, ions, elements, and organic and inorganic compound...

Cold Temperature Effects on Speciated VOC Emissions from modern GDI Light Duty Truck

EPA Science Inventory

Although gasoline direct injection (GDI) vehicles represent nearly half of the light-duty vehicle market share, few studies have reported speciated volatile organic compounds (VOCs) in GDI vehicle exhaust emissions. In this study, speciated VOC emissions were characterized from t...

The development of exhaust speciation profiles for commercial jet engines.

DOT National Transportation Integrated Search

2007-10-01

This study reports the emissions of CO, CO2, NOx, Particulate Matter (PM) mass, : speciated PM and speciated hydrocarbons at six thrust settings: 4%, 7%, 30%, 40%, 65% : and 85%, measured from both engines on four parked 737 aircraft at the Oakland :...

Geography, assortative mating, and the effects of sexual selection on speciation with gene flow.

PubMed

Servedio, Maria R

2016-01-01

Theoretical and empirical research on the evolution of reproductive isolation have both indicated that the effects of sexual selection on speciation with gene flow are quite complex. As part of this special issue on the contributions of women to basic and applied evolutionary biology, I discuss my work on this question in the context of a broader assessment of the patterns of sexual selection that lead to, versus inhibit, the speciation process, as derived from theoretical research. In particular, I focus on how two factors, the geographic context of speciation and the mechanism leading to assortative mating, interact to alter the effect that sexual selection through mate choice has on speciation. I concentrate on two geographic contexts: sympatry and secondary contact between two geographically separated populations that are exchanging migrants and two mechanisms of assortative mating: phenotype matching and separate preferences and traits. I show that both of these factors must be considered for the effects of sexual selection on speciation to be inferred.

Sympatric speciation as a consequence of male pregnancy in seahorses

PubMed Central

Jones, Adam G.; Moore, Glenn I.; Kvarnemo, Charlotta; Walker, DeEtte; Avise, John C.

2003-01-01

The phenomenon of male pregnancy in the family Syngnathidae (seahorses, pipefishes, and sea dragons) undeniably has sculpted the course of behavioral evolution in these fishes. Here we explore another potentially important but previously unrecognized consequence of male pregnancy: a predisposition for sympatric speciation. We present microsatellite data on genetic parentage that show that seahorses mate size-assortatively in nature. We then develop a quantitative genetic model based on these empirical findings to demonstrate that sympatric speciation indeed can occur under this mating regime in response to weak disruptive selection on body size. We also evaluate phylogenetic evidence bearing on sympatric speciation by asking whether tiny seahorse species are sister taxa to large sympatric relatives. Overall, our results indicate that sympatric speciation is a plausible mechanism for the diversification of seahorses, and that assortative mating (in this case as a result of male parental care) may warrant broader attention in the speciation process for some other taxonomic groups as well. PMID:12732712

Ephemeral ecological speciation and the latitudinal biodiversity gradient.

PubMed

Cutter, Asher D; Gray, Jeremy C

2016-10-01

The richness of biodiversity in the tropics compared to high-latitude parts of the world forms one of the most globally conspicuous patterns in biology, and yet few hypotheses aim to explain this phenomenon in terms of explicit microevolutionary mechanisms of speciation and extinction. We link population genetic processes of selection and adaptation to speciation and extinction by way of their interaction with environmental factors to drive global scale macroecological patterns. High-latitude regions are both cradle and grave with respect to species diversification. In particular, we point to a conceptual equivalence of "environmental harshness" and "hard selection" as eco-evolutionary drivers of local adaptation and ecological speciation. By describing how ecological speciation likely occurs more readily at high latitudes, with such nascent species especially prone to extinction by fusion, we derive the ephemeral ecological speciation hypothesis as an integrative mechanistic explanation for latitudinal gradients in species turnover and the net accumulation of biodiversity. © 2016 The Author(s). Evolution © 2016 The Society for the Study of Evolution.

Minimal effects of latitude on present-day speciation rates in New World birds

PubMed Central

Rabosky, Daniel L.; Title, Pascal O.; Huang, Huateng

2015-01-01

The tropics contain far greater numbers of species than temperate regions, suggesting that rates of species formation might differ systematically between tropical and non-tropical areas. We tested this hypothesis by reconstructing the history of speciation in New World (NW) land birds using BAMM, a Bayesian framework for modelling complex evolutionary dynamics on phylogenetic trees. We estimated marginal distributions of present-day speciation rates for each of 2571 species of birds. The present-day rate of speciation varies approximately 30-fold across NW birds, but there is no difference in the rate distributions for tropical and temperate taxa. Using macroevolutionary cohort analysis, we demonstrate that clades with high tropical membership do not produce species more rapidly than temperate clades. For nearly any value of present-day speciation rate, there are far more species in the tropics than the temperate zone. Any effects of latitude on speciation rate are marginal in comparison to the dramatic variation in rates among clades. PMID:26019156

Speciation by Symbiosis: the Microbiome and Behavior

PubMed Central

Shropshire, J. Dylan

2016-01-01

ABSTRACT Species are fundamental units of comparison in biology. The newly discovered importance and ubiquity of host-associated microorganisms are now stimulating work on the roles that microbes can play in animal speciation. We previously synthesized the literature and advanced concepts of speciation by symbiosis with notable attention to hybrid sterility and lethality. Here, we review recent studies and relevant data on microbes as players in host behavior and behavioral isolation, emphasizing the patterns seen in these analyses and highlighting areas worthy of additional exploration. We conclude that the role of microbial symbionts in behavior and speciation is gaining exciting traction and that the holobiont and hologenome concepts afford an evolving intellectual framework to promote research and intellectual exchange between disciplines such as behavior, microbiology, genetics, symbiosis, and speciation. Given the increasing centrality of microbiology in macroscopic life, microbial symbiosis is arguably the most neglected aspect of animal and plant speciation, and studying it should yield a better understanding of the origin of species. PMID:27034284

Speciation by Symbiosis: the Microbiome and Behavior.

PubMed

Shropshire, J Dylan; Bordenstein, Seth R

2016-03-31

Species are fundamental units of comparison in biology. The newly discovered importance and ubiquity of host-associated microorganisms are now stimulating work on the roles that microbes can play in animal speciation. We previously synthesized the literature and advanced concepts of speciation by symbiosis with notable attention to hybrid sterility and lethality. Here, we review recent studies and relevant data on microbes as players in host behavior and behavioral isolation, emphasizing the patterns seen in these analyses and highlighting areas worthy of additional exploration. We conclude that the role of microbial symbionts in behavior and speciation is gaining exciting traction and that the holobiont and hologenome concepts afford an evolving intellectual framework to promote research and intellectual exchange between disciplines such as behavior, microbiology, genetics, symbiosis, and speciation. Given the increasing centrality of microbiology in macroscopic life, microbial symbiosis is arguably the most neglected aspect of animal and plant speciation, and studying it should yield a better understanding of the origin of species. Copyright © 2016 Shropshire and Bordenstein.

Evidence of plutonium bioavailability in pristine freshwaters of a karst system of the Swiss Jura Mountains

NASA Astrophysics Data System (ADS)

Cusnir, Ruslan; Christl, Marcus; Steinmann, Philipp; Bochud, François; Froidevaux, Pascal

2017-06-01

The interaction of trace environmental plutonium with dissolved natural organic matter (NOM) plays an important role on its mobility and bioavailability in freshwater environments. Here we explore the speciation and biogeochemical behavior of Pu in freshwaters of the karst system in the Swiss Jura Mountains. Chemical extraction and ultrafiltration methods were complemented by diffusive gradients in thin films technique (DGT) to measure the dissolved and bioavailable Pu fraction in water. Accelerator mass spectrometry (AMS) was used to accurately determine Pu in this pristine environment. Selective adsorption of Pu (III, IV) on silica gel showed that 88% of Pu in the mineral water is found in +V oxidation state, possibly in a highly soluble [PuO2+(CO3)n]m- form. Ultrafiltration experiments at 10 kDa yielded a similar fraction of colloid-bound Pu in the organic-rich and in mineral water (18-25%). We also found that the concentrations of Pu measured by DGT in mineral water are similar to the bulk concentration, suggesting that dissolved Pu is readily available for biouptake. Sequential elution (SE) of Pu from aquatic plants revealed important co-precipitation of potentially labile Pu (60-75%) with calcite fraction within outer compartment of the plants. Hence, we suggest that plutonium is fully available for biological uptake in both mineral and organic-rich karstic freshwaters.

How reliable are environmental data on 'orphan' elements? The case of bismuth concentrations in surface waters.

PubMed

Filella, Montserrat

2010-01-01

Like all elements of the periodic table, bismuth is ubiquitously distributed throughout the environment as a result of natural processes and human activities. It is present as Bi(III) in environmental, biological and geochemical samples. Although bismuth and its compounds are considered to be non-toxic to humans, its increasing use as a replacement for lead has highlighted how little is known about its environmental and ecotoxicological behaviour. In this first critical review paper on the existing information on bismuth occurrence in natural waters, 125 papers on fresh and marine waters have been collated. Although the initial objective of this study was to establish the range of the typical concentrations of total dissolved bismuth in natural waters, this proved impossible to achieve due to the wide, and hitherto unexplained, dispersion of published data. Since analytical limitations might be one of the reasons underlying value dispersion, new analytical methods published since 2000--intended to be applied to natural waters--have also been reviewed. Disappointingly, the detection limits of the bulk of them are well above those required; they are thus of limited usefulness. Analysis of the existing information on bismuth in secondary references (i.e., books, review chapters) and on its chemical speciation in seawater revealed that the uncritical reproduction of old data is a widespread practice.

Iron isotope biogeochemistry of Neoproterozoic marine shales

NASA Astrophysics Data System (ADS)

Kunzmann, Marcus; Gibson, Timothy M.; Halverson, Galen P.; Hodgskiss, Malcolm S. W.; Bui, Thi Hao; Carozza, David A.; Sperling, Erik A.; Poirier, André; Cox, Grant M.; Wing, Boswell A.

2017-07-01

Iron isotopes have been widely applied to investigate the redox evolution of Earth's surface environments. However, it is still unclear whether iron cycling in the water column or during diagenesis represents the major control on the iron isotope composition of sediments and sedimentary rocks. Interpretation of isotopic data in terms of oceanic redox conditions is only possible if water column processes dominate the isotopic composition, whereas redox interpretations are less straightforward if diagenetic iron cycling controls the isotopic composition. In the latter scenario, iron isotope data is more directly related to microbial processes such as dissimilatory iron reduction. Here we present bulk rock iron isotope data from late Proterozoic marine shales from Svalbard, northwestern Canada, and Siberia, to better understand the controls on iron isotope fractionation in late Proterozoic marine environments. Bulk shales span a δ 56Fe range from -0.45 ‰ to +1.04 ‰ . Although δ 56Fe values show significant variation within individual stratigraphic units, their mean value is closer to that of bulk crust and hydrothermal iron in samples post-dating the ca. 717-660 Ma Sturtian glaciation compared to older samples. After correcting for the highly reactive iron content in our samples based on iron speciation data, more than 90% of the calculated δ 56Fe compositions of highly reactive iron falls in the range from ca. -0.8 ‰ to +3 ‰ . An isotope mass-balance model indicates that diagenetic iron cycling can only change the isotopic composition of highly reactive iron by < 1 ‰ , suggesting that water column processes, namely the degree of oxidation of the ferrous seawater iron reservoir, control the isotopic composition of highly reactive iron. Considering a long-term decrease in the isotopic composition of the iron source to the dissolved seawater Fe(II) reservoir to be unlikely, we offer two possible explanations for the Neoproterozoic δ 56Fe trend. First, a decreasing supply of Fe(II) to the ferrous seawater iron reservoir could have caused the reservoir to decrease in size, allowing a higher degree of partial oxidation, irrespective of increasing environmental oxygen levels. Alternatively, increasing oxygen levels would have led to a higher proportion of Fe(II) being oxidized, without decreasing the initial size of the ferrous seawater iron pool. We consider the latter explanation as the most likely. According to this hypothesis, the δ 56Fe record reflects the redox evolution of Earth's surface environments. δ 56Fe values in pre-Sturtian samples significantly heavier than bulk crust and hydrothermal iron imply partial oxidation of a ferrous seawater iron reservoir. In contrast, mean δ 56Fe values closer to that of hydrothermal iron in post-Sturtian shales reflects oxidation of a larger proportion of the ferrous seawater iron reservoir, and by inference, higher environmental oxygen levels. Nevertheless, significant iron isotopic variation in post-Sturtian shales suggest redox heterogeneity and possibly a dominantly anoxic deep ocean, consistent with results from recent studies using iron speciation and redox sensitive trace metals. However, the interpretation of generally increasing environmental oxygen levels after the Sturtian glaciation highlights the need to better understand the sensitivity of different redox proxies to incremental changes in oxygen levels to enable us to reconcile results from different paleoredox proxies.

Speciation via floral heterochrony and presumed mycorrhizal host switching of endemic butterfly orchids on the Azorean archipelago.

PubMed

Bateman, Richard M; Rudall, Paula J; Bidartondo, Martin I; Cozzolino, Salvatore; Tranchida-Lombardo, Valentina; Carine, Mark A; Moura, Mónica

2014-06-01

• Premise of the study: Most orchid species native to the Macaronesian islands reflect immigration from western Europe or North Africa followed by anagenesis. The only putative exception is the butterfly orchids (Platanthera) of the Azores, where three species apparently reflect at least one cladogenetic speciation event. This multidisciplinary study explores the origin, speciation, phenotypic, and genotypic cohesion of these Azorean species and their mainland relatives.• Methods: Plants of Platanthera from 30 localities spanning all nine Azorean islands were compared with those of four continental European relatives for 38 morphometric characters; substantial subsets were also analyzed for plastid microsatellites, and for nrITS of both the orchids and their mycorrhizae.• Key results: Although the three Azorean and four mainland species are all readily distinguished morphometrically using several floral characters, and hybridization appears rare, divergence in ITS and especially plastid sequences is small. Despite occupying similar laurisilva habitats, the Azorean species differ radically in the identities and diversity of their mycorrhizal partners; specialism apparently increases rarity.• Conclusions: Although morphological evidence suggests two invasions of the islands from NW Africa and/or SW Europe, ITS data imply only one. As the molecular data are unable to distinguish among the potential mainland ancestors, two scenarios of relationship are explored that imply different ancestors. Both scenarios require both anagenetic and cladogenetic speciation events, involving homoplastic shifts in overall flower size and (often substantial) changes in the relative dimensions of individual floral organs. Limited genotypic divergence among the three species compared with greater phenotypic divergence suggests comparatively recent speciation. Mycorrhizae may be the most critical factor dictating the respective ecological tolerances, and thus the relative frequencies, of these species. The recent IUCN Red-List amalgamation of Azorean Platanthera taxa into a single species urgently requires reappraisal, as P. micrantha is an excellent indicator species of seminatural laurisilva forest and P. azorica is arguably Europe's rarest orchid. © 2014 Botanical Society of America, Inc.

Graphene oxide-TiO2 composite solid phase extraction combined with graphite furnace atomic absorption spectrometry for the speciation of inorganic selenium in water samples.

PubMed

Zhang, Yanan; Chen, Beibei; Wu, Shaowei; He, Man; Hu, Bin

2016-07-01

In this paper, a method of graphene oxide (GO)-TiO2 composite solid phase extraction followed by graphite furnace atomic absorption spectrometry (GFAAS) detection was proposed for the speciation of inorganic selenium in environmental waters. The adsorption behavior of inorganic Se(IV) and Se(VI) on the GO-TiO2(1:1) composite was investigated. It was found that Se(IV) was quantitatively retained on the GO-TiO2 composites within a wide pH range of 0.5-10, while Se(VI) was quantitatively adsorbed on GO-TiO2(1:1) composite at pH 0.5-2, and no obvious adsorption of Se(VI) within the pH range of 4-10 was found. By selecting pH 6.0, Se(IV) could be easily determined. After reduction of Se(VI), total Se was determined by the proposed method, and Se(VI) was calculated as the difference between the total Se and Se(IV). The factors affecting the separation/preconcentration of Se(IV) and Se(VI) were studied. Under the optimum conditions, the isothermal adsorption of Se(IV) on the GO-TiO2(1:1) composite fitted Langmuir model; a linear range over 0.1-12ngmL(-1) was obtained. The limit of detection (LOD) and precision of the method for Se(IV) was 0.04ngmL(-1) and 9.4% (cSe(IV)=0.5ngmL(-1), n=7), respectively. In order to verify the accuracy of the method, a standard water sample (GSBZ50031-94) was analyzed, and the determined value was in a good agreement to the certified value. The established method was applied to inorganic Se speciation in environmental water samples and the recovery of 87.4-102% was obtained for the spiked samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Field Evaluation Of Arsenic Speciation In Sediments At The Ground Water/Surface Water Interface

EPA Science Inventory

The speciation and mineralogy of sediments contaminated with arsenic at the ground water/surface water interface of the Ft. Devens Super Fund Site in Ft. Devens, MA were determined using X-ray absorption fine structure and X-ray diffraction spectroscopy. Speciation and mineralog...

Gas and liquid chromatography with inductively coupled plasma mass spectrometry detection for environmental speciation analysis — advances and limitations

NASA Astrophysics Data System (ADS)

Szpunar, Joanna; McSheehy, Shona; Połeć, Kasia; Vacchina, Véronique; Mounicou, Sandra; Rodriguez, Isaac; Łobiński, Ryszard

2000-07-01

Recent advances in the coupling of gas chromatography (GC) and high performance liquid chromatography (HPLC) with inductively coupled plasma mass spectrometry (ICP MS) and their role in trace element speciation analysis of environmental materials are presented. The discussion is illustrated with three research examples concerning the following topics: (i) development and coupling of multicapillary microcolumn GC with ICP MS for speciation of organotin in sediment and biological tissue samples; (ii) speciation of arsenic in marine algae by size-exclusion-anion-exchange HPLC-ICP MS; and (iii) speciation of cadmium in plant cell cultures by size-exclusion HPLC-ICP MS. Particular attention is paid to the problem of signal identification in ICP MS chromatograms; the potential of electrospray MS/MS for this purpose is highlighted.

Chromosomes, conflict, and epigenetics: chromosomal speciation revisited.

PubMed

Brown, Judith D; O'Neill, Rachel J

2010-01-01

Since Darwin first noted that the process of speciation was indeed the "mystery of mysteries," scientists have tried to develop testable models for the development of reproductive incompatibilities-the first step in the formation of a new species. Early theorists proposed that chromosome rearrangements were implicated in the process of reproductive isolation; however, the chromosomal speciation model has recently been questioned. In addition, recent data from hybrid model systems indicates that simple epistatic interactions, the Dobzhansky-Muller incompatibilities, are more complex. In fact, incompatibilities are quite broad, including interactions among heterochromatin, small RNAs, and distinct, epigenetically defined genomic regions such as the centromere. In this review, we will examine both classical and current models of chromosomal speciation and describe the "evolving" theory of genetic conflict, epigenetics, and chromosomal speciation.

XAS Studies of Se Speciation in Selenite-Fed Rats

PubMed Central

Weekley, Claire M.; Aitken, Jade B.; Witting, Paul K.; Harris, Hugh H.

2014-01-01

The biological activity of selenium is dependent on its chemical form. Therefore, knowledge of Se chemistry in vivo is required for efficacious use of selenium compounds in disease prevention and treatment. Using X-ray absorption spectroscopy, Se speciation in the kidney, liver, heart, spleen, testis and red blood cells of rats fed control (~0.3 ppm Se) or selenite-supplemented (1 ppm or 5 ppm Se) diets for 3 or 6 weeks, was investigated. X-ray absorption spectroscopy revealed the presence of Se–Se and Se–C species in the kidney and liver, and Se–S species in the kidney, but not the liver. X-ray absorption near edge structure (XANES) spectra showed that there was variation in speciation in the liver and kidneys, but Se speciation was much more uniform in the remaining organs. Using principal component analysis (PCA) to interpret the Se K-edge X-ray absorption spectra, we were able to directly compare the speciation of Se in two different models of selenite metabolism – human lung cancer cells and rat tissues. The effects of Se dose, tissue type and duration of diet on selenium speciation in rat tissues were investigated, and a relationship between the duration of the diet (3 weeks versus 6 weeks) and selenium speciation was observed. PMID:25363824

Intercomparison of analytical methods for arsenic speciation in human urine.

PubMed Central

Crecelius, E; Yager, J

1997-01-01

An intercomparison exercise was conducted for the quantification of arsenic species in spiked human urine. The primary objective of the exercise was to determine the variance among laboratories in the analysis of arsenic species such as inorganic As (As+3 and As+5), monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA). Laboratories that participated had previous experience with arsenic speciation analysis. The results of this interlaboratory comparison are encouraging. There is relatively good agreement on the concentrations of these arsenic species in urine at concentrations that are relevant to research on the metabolism of arsenic in humans and other mammals. Both the accuracy and precision are relatively poor for arsenic concentrations of less than about 5 micrograms/l. PMID:9288500

Pollinator-driven ecological speciation in plants: new evidence and future perspectives

PubMed Central

Van der Niet, Timotheüs; Peakall, Rod; Johnson, Steven D.

2014-01-01

Background The hypothesis that pollinators have been important drivers of angiosperm diversity dates back to Darwin, and remains an important research topic today. Mounting evidence indicates that pollinators have the potential to drive diversification at several different stages of the evolutionary process. Microevolutionary studies have provided evidence for pollinator-mediated floral adaptation, while macroevolutionary evidence supports a general pattern of pollinator-driven diversification of angiosperms. However, the overarching issue of whether, and how, shifts in pollination system drive plant speciation represents a critical gap in knowledge. Bridging this gap is crucial to fully understand whether pollinator-driven microevolution accounts for the observed macroevolutionary patterns. Testable predictions about pollinator-driven speciation can be derived from the theory of ecological speciation, according to which adaptation (microevolution) and speciation (macroevolution) are directly linked. This theory is a particularly suitable framework for evaluating evidence for the processes underlying shifts in pollination systems and their potential consequences for the evolution of reproductive isolation and speciation. Scope This Viewpoint paper focuses on evidence for the four components of ecological speciation in the context of plant-pollinator interactions, namely (1) the role of pollinators as selective agents, (2) floral trait divergence, including the evolution of ‘pollination ecotypes‘, (3) the geographical context of selection on floral traits, and (4) the role of pollinators in the evolution of reproductive isolation. This Viewpoint also serves as the introduction to a Special Issue on Pollinator-Driven Speciation in Plants. The 13 papers in this Special Issue range from microevolutionary studies of ecotypes to macroevolutionary studies of historical ecological shifts, and span a wide range of geographical areas and plant families. These studies further illustrate innovative experimental approaches, and they employ modern tools in genetics and floral trait quantification. Future advances to the field require better quantification of selection through male fitness and pollinator isolation, for instance by exploiting next-generation sequencing technologies. By combining these new tools with strategically chosen study systems, and smart experimental design, we predict that examples of pollinator-driven speciation will be among the most widespread and compelling of all cases of ecological speciation. PMID:24418954

PRINCIPLES OF SYNCHROTRON TECHNIQUES, POTENTIAL AND LIMITATIONS

EPA Science Inventory

Once environmental contaminants, such as arsenic, chromium, cadmium and lead, are detected, the problem becomes how to deal with them. For the past decade, researchers at the US EPA in Cincinnati have been employing synchrotron speciation methods to determine the exact chemical f...

SEPARATION AND DETECTION OF THREE ARYLTINS BY CAPILLARY ELECTROPHORESIS-UV/VIS DIODE ARRAY

EPA Science Inventory

The trialkyltins and triphenyltins have widespread application as fungicides, antifouling coatings for porous surfaces, herbicides, insecticides, and generic biocides. Due to the varied toxicity of each species of organotins, it is important that methods address the speciation of...

Demographic modelling with whole-genome data reveals parallel origin of similar Pundamilia cichlid species after hybridization.

PubMed

Meier, Joana I; Sousa, Vitor C; Marques, David A; Selz, Oliver M; Wagner, Catherine E; Excoffier, Laurent; Seehausen, Ole

2017-01-01

Modes and mechanisms of speciation are best studied in young species pairs. In older taxa, it is increasingly difficult to distinguish what happened during speciation from what happened after speciation. Lake Victoria cichlids in the genus Pundamilia encompass a complex of young species and polymorphic populations. One Pundamilia species pair, P. pundamilia and P. nyererei, is particularly well suited to study speciation because sympatric population pairs occur with different levels of phenotypic differentiation and reproductive isolation at different rocky islands within the lake. Genetic distances between allopatric island populations of the same nominal species often exceed those between the sympatric species. It thus remained unresolved whether speciation into P. nyererei and P. pundamilia occurred once, followed by geographical range expansion and interspecific gene flow in local sympatry, or if the species pair arose repeatedly by parallel speciation. Here, we use genomic data and demographic modelling to test these alternative evolutionary scenarios. We demonstrate that gene flow plays a strong role in shaping the observed patterns of genetic similarity, including both gene flow between sympatric species and gene flow between allopatric populations, as well as recent and early gene flow. The best supported model for the origin of P. pundamilia and P. nyererei population pairs at two different islands is one where speciation happened twice, whereby the second speciation event follows shortly after introgression from an allopatric P. nyererei population that arose earlier. Our findings support the hypothesis that very similar species may arise repeatedly, potentially facilitated by introgressed genetic variation. © 2016 John Wiley & Sons Ltd.

Ecological speciation in the tropics: insights from comparative genetic studies in Amazonia

PubMed Central

Beheregaray, Luciano B.; Cooke, Georgina M.; Chao, Ning L.; Landguth, Erin L.

2015-01-01

Evolution creates and sustains biodiversity via adaptive changes in ecologically relevant traits. Ecologically mediated selection contributes to genetic divergence both in the presence or absence of geographic isolation between populations, and is considered an important driver of speciation. Indeed, the genetics of ecological speciation is becoming increasingly studied across a variety of taxa and environments. In this paper we review the literature of ecological speciation in the tropics. We report on low research productivity in tropical ecosystems and discuss reasons accounting for the rarity of studies. We argue for research programs that simultaneously address biogeographical and taxonomic questions in the tropics, while effectively assessing relationships between reproductive isolation and ecological divergence. To contribute toward this goal, we propose a new framework for ecological speciation that integrates information from phylogenetics, phylogeography, population genomics, and simulations in evolutionary landscape genetics (ELG). We introduce components of the framework, describe ELG simulations (a largely unexplored approach in ecological speciation), and discuss design and experimental feasibility within the context of tropical research. We then use published genetic datasets from populations of five codistributed Amazonian fish species to assess the performance of the framework in studies of tropical speciation. We suggest that these approaches can assist in distinguishing the relative contribution of natural selection from biogeographic history in the origin of biodiversity, even in complex ecosystems such as Amazonia. We also discuss on how to assess ecological speciation using ELG simulations that include selection. These integrative frameworks have considerable potential to enhance conservation management in biodiversity rich ecosystems and to complement historical biogeographic and evolutionary studies of tropical biotas. PMID:25653668

Modeling Non-Steady Isotopologue and Isotopomer Speciation and Fractionation during Denitrification in Soils

NASA Astrophysics Data System (ADS)

Maggi, F.; Riley, W. J.

2009-12-01

The composition and location of 15N atoms on N2O isotopomers and isotopologues during isotope speciation has been used to characterize soil biological N cycling and N2O surface emissions. Although there exist few experimental observations, no attempt has been made to model N2O isotopomer speciation. The mathematical treatment of biological kinetic reactions in isotopic applications normally makes use of first-order and quasi steady-state complexation assumptions without taking into account changes in enzyme concentration, reaction stoichiometry, and isotopologue and isotopomer speciation. When multiatomic isotopically-labeled reactants are used in a multi-molecurar reaction, these assumptions may fail since they always lead to a constant fractionation factor and cannot describe speciation of isotopologues and isotopomers. We have developed a mathematical framework that is capable of describing isotopologue and isotopmer speciation and fractionation under the assumption of non-steady complexation during biological kinetic reactions that overcome the limitations mentioned above. This framework was applied to a case study of non-steady (variable and inverse) isotopic effects observed during N2O production and consumption in soils. Our mathematical treatment has led to generalized kinetic equations which replicate experimental observations with high accuracy and help interpret non-steady isotopic effects and isotopologue and isotopomer speciation. The kinetic equations introduced and applied here have general validity in describing isotopic effects in any biochemical reactions by considering: changing enzyme concentrations, mass and isotope conservation, and reaction stoichiometry. The equations also describe speciation of any isotopologue and isotopomer product from any isotopologue and isotopmer reactant.

Fracture Toughness Properties of Gd123 Superconducting Bulks

NASA Astrophysics Data System (ADS)

Fujimoto, H.; Murakami, A.

Fracture toughness properties of melt growth GdBa2Cu3Ox (Gd123) large single domain superconducting bulks with Ag2O of 10 wt% and Pt of 0.5 wt%; 45 mm in diameter and 25 mm in thickness with low void density were evaluated at 77 K through flexural tests of specimens cut from the bulks, and compared to those of a conventional Gd123 with voids. The densified Gd123 bulks were prepared with a seeding and temperature gradient method; first melt processed in oxygen, then crystal growth in air; two-step regulated atmosphere heat treatment. The plane strain fracture toughness, KIC was obtained by the three point flexure test of the specimens with through precrack, referring to the single edge pre-cracked beam (SEPB) method, according to the JIS-R-1607, Testing Methods for Fracture Toughness of High Performance Ceramics. The results show that the fracture toughness of the densified Gd123 bulk with low void density was higher than that of the standard Gd123 bulk with voids, as well as the flexural strength previously reported. We also compared the fracture toughness of as-grown bulks with that of annealed bulks. The relation between the microstructure and the fracture toughness of the Gd123 bulk was clearly shown.

Fast arsenic speciation in water by on-site solid phase extraction and high-resolution continuum source graphite furnace atomic absorption spectrometry

NASA Astrophysics Data System (ADS)

Mihucz, Victor G.; Bencs, László; Koncz, Kornél; Tatár, Enikő; Weiszburg, Tamás; Záray, Gyula

2017-02-01

A method of high-resolution continuum source graphite furnace atomic absorption spectrometry (HR-CS-GFAAS), combined with on-site separation/solid phase extraction (SPE) has been developed for the speciation of inorganic As (iAs) in geothermal and drinking water samples. The HR-CS-GFAAS calibration curves were linear up to 200 μg/L As, but using second order polynomial fitting, accurate calibration could be performed up to 500 μg/L. It has been demonstrated that sample pH should not be higher than 8 for an accurate speciation of As(V) with a recovery of ≈ 95%. Geothermal water had fairly high salt content (≈ 2200 mg/L) due to the presence of chlorides and sulfates at mg/L levels. Therefore, a two-fold dilution of these types of samples before SPE is recommended, especially, for total As determinations, when the As concentration is as high as 400 μg/L. For drinking water, sampled from public wells with records of As concentrations higher than the 10 μg/L in the past, the reduction of As contamination below the WHO's health limit value could be observed. However, the electrical conductivity was close to 2500 μS/cm, i.e., the guideline limit for drinking water, which was due to their higher chloride content. The proposed fit-for-purpose SPE-HR-CS-GFAAS method could be a candidate for screening drinking water quality.

Evaluation of comprehensive two-dimensional gas chromatography with flame photometric detection: potential application for sulfur speciation in shale oil.

PubMed

Mitrevski, Blagoj; Amer, Mohammad W; Chaffee, Alan L; Marriott, Philip J

2013-11-25

Flame photometric detection in the sulfur channel has been evaluated for sulfur speciation and quantification in comprehensive two-dimensional gas chromatography [GC × GC-FPD(S)] for S-compound speciation in shale extracts. Signal non-linearity and potential quenching effects were reportedly major limitations of this detector for analysis of sulfur in complex matrices. However, reliable linear relationships with correlation coefficient >0.99 can be obtained if the sum of the square root of each modulation slice in GC × GC is plotted vs. sulfur concentration. Furthermore, the quenching effects are reduced due to essentially complete separation of S-containing components from the hydrocarbon matrix. An increase of S/N of up to 150 times has been recorded for benzothiophene and dibenzothiophene in GC × GC-FPD when compared to GC-FPD due to the modulation process. As a consequence, 10 times lower detection limits were observed in the former mode. The applicability of the method was demonstrated using shale oil sample extracts. Three sulfur classes were completely separated and the target class (thiophenes) was successfully quantified after the rest of the sample was diverted to the second detector by using a heart-cut strategy. Based on the proposed method, 70% of the sulfur in the shale oil was assigned to the thiophenes, 24% to benzothiophenes, and 5% to dibenzothiophene compounds. Copyright © 2013 Elsevier B.V. All rights reserved.

Sample preparation for arsenic speciation analysis in baby food by generation of substituted arsines with atomic absorption spectrometry detection.

PubMed

Huber, Charles S; Vale, Maria Goreti R; Dessuy, Morgana B; Svoboda, Milan; Musil, Stanislav; Dědina, Jiři

2017-12-01

A slurry sampling procedure for arsenic speciation analysis in baby food by arsane generation, cryogenic trapping and detection with atomic absorption spectrometry is presented. Several procedures were tested for slurry preparation, including different reagents (HNO 3 , HCl and tetramethylammonium hydroxide - TMAH) and their concentrations, water bath heating and ultrasound-assisted agitation. The best results for inorganic arsenic (iAs) and dimethylarsinate (DMA) were reached when using 3molL -1 HCl under heating and ultrasound-assisted agitation. The developed method was applied for the analysis of five porridge powder and six baby meal samples. The trueness of the method was checked with a certified reference material (CRM) of total arsenic (tAs), iAs and DMA in rice (ERM-BC211). Arsenic recoveries (mass balance) for all samples and CRM were performed by the determination of the tAs by inductively coupled plasma mass spectrometry (ICP-MS) after microwave-assisted digestion and its comparison against the sum of the results from the speciation analysis. The relative limits of detection were 0.44, 0.24 and 0.16µgkg -1 for iAs, methylarsonate and DMA, respectively. The concentrations of the most toxic arsenic species (iAs) in the analyzed baby food samples ranged between 4.2 and 99µgkg -1 which were below the limits of 300, 200 and 100µgkg -1 set by the Brazilian, Chinese and European legislation, respectively. Copyright © 2017 Elsevier B.V. All rights reserved.

Systems and Methods for Implementing Bulk Metallic Glass-Based Macroscale Compliant Mechanisms

NASA Technical Reports Server (NTRS)

Hofmann, Douglas C. (Inventor); Agnes, Gregory (Inventor)

2017-01-01

Systems and methods in accordance with embodiments of the invention implement bulk metallic glass-based macroscale compliant mechanisms. In one embodiment, a bulk metallic glass-based macroscale compliant mechanism includes: a flexible member that is strained during the normal operation of the compliant mechanism; where the flexible member has a thickness of 0.5 mm; where the flexible member comprises a bulk metallic glass-based material; and where the bulk metallic glass-based material can survive a fatigue test that includes 1000 cycles under a bending loading mode at an applied stress to ultimate strength ratio of 0.25.

Speciation and Toxic Emissions from On road Vehicles, and Particulate Matter Emissions from Light-Duty Gasoline Vehicles in MOVES201X

EPA Science Inventory

Updated methane, non-methane organic gas, and volatile organic compound calculations based on speciation data. Updated speciation and toxic emission rates for new model year 2010 and later heavy-duty diesel engines. Updated particulate matter emission rates for 2004 and later mod...

Sexual selection drives speciation in an Amazonian frog

USGS Publications Warehouse

Boul, K.E.; Funk, W.C.; Darst, C.R.; Cannatella, D.C.; Ryan, M.J.

2007-01-01

One proposed mechanism of speciation is divergent sexual selection, whereby divergence in female preferences and male signals results in behavioural isolation. Despite the appeal of this hypothesis, evidence for it remains inconclusive. Here, we present several lines of evidence that sexual selection is driving behavioural isolation and speciation among populations of an Amazonian frog (Physalaemus petersi). First, sexual selection has promoted divergence in male mating calls and female preferences for calls between neighbouring populations, resulting in strong behavioural isolation. Second, phylogenetic analysis indicates that populations have become fixed for alternative call types several times throughout the species' range, and coalescent analysis rejects genetic drift as a cause for this pattern, suggesting that this divergence is due to selection. Finally, gene flow estimated with microsatellite loci is an average of 30 times lower between populations with different call types than between populations separated by a similar geographical distance with the same call type, demonstrating genetic divergence and incipient speciation. Taken together, these data provide strong evidence that sexual selection is driving behavioural isolation and speciation, supporting sexual selection as a cause for speciation in the wild. ?? 2006 The Royal Society.

A gas chromatographic method for the determination of bicarbonate and dissolved gases

USDA-ARS?s Scientific Manuscript database

A gas chromatographic method for the rapid determination of aqueous carbon dioxide and its speciation into solvated carbon dioxide and bicarbonate is presented. One-half mL samples are injected through a rubber septum into 20-mL vials that are filled with 9.5 mL of 0.1 N HCl. A one mL portion of the...

Feasibility of coupling a thermal/optical carbon analyzer to a quadrupole mass spectrometer for enhanced PM2.5 speciation.

PubMed

Riggio, Gustavo M; Chow, Judith C; Cropper, Paul M; Wang, Xiaoliang; Yatavelli, Reddy L N; Yang, Xufei; Watson, John G

2018-05-01

A thermal/optical carbon analyzer (TOA), normally used for quantification of organic carbon (OC) and elemental carbon (EC) in PM 2.5 (fine particulate matter) speciation networks, was adapted to direct thermally evolved gases to an electron impact quadrupole mass spectrometer (QMS), creating a TOA-QMS. This approach produces spectra similar to those obtained by the Aerodyne aerosol mass spectrometer (AMS), but the ratios of the mass to charge (m/z) signals differ and must be remeasured using laboratory-generated standards. Linear relationships are found between TOA-QMS signals and ammonium (NH 4 + ), nitrate (NO 3 - ), and sulfate (SO 4 2- ) standards. For ambient samples, however, positive deviations are found for SO 4 2- , compensated by negative deviations for NO 3 - , at higher concentrations. This indicates the utility of mixed-compound standards for calibration or separate calibration curves for low and high ion concentrations. The sum of the QMS signals across all m/z after removal of the NH 4 + , NO 3 - , and SO 4 2- signals was highly correlated with the carbon content of oxalic acid (C₂H₂O₄) standards. For ambient samples, the OC derived from the TOA-QMS method was the same as the OC derived from the standard IMPROVE_A TOA method. This method has the potential to reduce complexity and costs for speciation networks, especially for highly polluted urban areas such as those in Asia and Africa. Ammonium, nitrate, and sulfate can be quantified by the same thermal evolution analysis applied to organic and elemental carbon. This holds the potential to replace multiple parallel filter samples and separate laboratory analyses with a single filter and a single analysis to account for a large portion of the PM 2.5 mass concentration.

Comparison of soil organic carbon speciation using C NEXAFS and CPMAS 13C NMR spectroscopy.

PubMed

Prietzel, Jörg; Müller, Svenja; Kögel-Knabner, Ingrid; Thieme, Jürgen; Jaye, Cherno; Fischer, Daniel

2018-07-01

We compared synchrotron-based C near-edge X-ray absorption fine structure (NEXAFS) and CPMAS 13 C nuclear magnetic resonance (NMR) spectroscopy with respect to their precision and accuracy to quantify different organic carbon (OC) species in defined mixtures of soil organic matter source compounds. We also used both methods to quantify different OC species in organic surface horizons of a Histic Leptosol as well as in mineral topsoil and subsoil horizons of two soils with different parent material, stage of pedogenesis, and OC content (Cambisol: 15-30 OC mgg -1 , Podzol: 0.9-7 OC mgg -1 ). CPMAS 13 C NMR spectroscopy was more accurate and precise (mean recovery of different C functional groups 96-103%) than C NEXAFS spectroscopy (mean recovery 92-113%). For organic surface and topsoil samples, NMR spectroscopy consistently yielded larger O-alkyl C percentages and smaller alkyl C percentages than C NEXAFS spectroscopy. For the Cambisol subsoil samples both methods performed well and showed similar C speciation results. NEXAFS spectroscopy yielded excellent spectra with a high signal-to-noise ratio also for OC-poor Podzol subsoil samples, whereas this was not the case for CPMAS 13 C NMR spectroscopy even after sample treatment with HF. Our results confirm the analytical power of CPMAS 13 C NMR spectroscopy for a reliable quantitative OC speciation in soils with >10mgOCg -1 . Moreover, they highlight the potential of synchrotron-based C NEXAFS spectroscopy as fast, non-invasive method to semi-quantify different C functional groups in soils with low C content (0.9-10mgg -1 ). Copyright © 2018 Elsevier B.V. All rights reserved.

A novel HTS magnetic levitation dining table

NASA Astrophysics Data System (ADS)

Lu, Yiyun; Huang, Huiying

2018-05-01

High temperature superconducting (HTS) bulk can levitate above or suspend below a permanent magnet stably. Many magnificent potential applications of HTS bulk are proposed by researchers. Until now, few reports have been found for real applications of HTS bulk. A complete set of small-scale HTS magnetic levitation table is proposed in the paper. The HTS magnetic levitation table includes an annular HTS magnetic levitation system which is composed of an annular HTS bulk array and an annular permanent magnet guideway (PMG). The annular PMG and the annular cryogenics vessel which used to maintain low temperature environment of the HTS bulk array are designed. 62 YBCO bulks are used to locate at the bottom of the annular vessel. A 3D-model finite element numerical method is used to design the HTS bulk magnetic levitation system. Equivalent magnetic levitation and guidance forces calculation rules are proposed aimed at the annular HTS magnetic levitation system stability. Based on the proposed method, levitation and guidance forces curves of the one YBCO bulk magnetic above PMG could be obtained. This method also can use to assist PMG design to check whether the designed PMG could reach the basic demand of the HTS magnetic levitation table.

On the distribution of interspecies correlation for Markov models of character evolution on Yule trees.

PubMed

Mulder, Willem H; Crawford, Forrest W

2015-01-07

Efforts to reconstruct phylogenetic trees and understand evolutionary processes depend fundamentally on stochastic models of speciation and mutation. The simplest continuous-time model for speciation in phylogenetic trees is the Yule process, in which new species are "born" from existing lineages at a constant rate. Recent work has illuminated some of the structural properties of Yule trees, but it remains mostly unknown how these properties affect sequence and trait patterns observed at the tips of the phylogenetic tree. Understanding the interplay between speciation and mutation under simple models of evolution is essential for deriving valid phylogenetic inference methods and gives insight into the optimal design of phylogenetic studies. In this work, we derive the probability distribution of interspecies covariance under Brownian motion and Ornstein-Uhlenbeck models of phenotypic change on a Yule tree. We compute the probability distribution of the number of mutations shared between two randomly chosen taxa in a Yule tree under discrete Markov mutation models. Our results suggest summary measures of phylogenetic information content, illuminate the correlation between site patterns in sequences or traits of related organisms, and provide heuristics for experimental design and reconstruction of phylogenetic trees. Copyright © 2014 Elsevier Ltd. All rights reserved.

Speciation of arsenic in marine food (Anemonia sulcata) by liquid chromatography coupled to inductively coupled plasma mass spectrometry and organic mass spectrometry.

PubMed

Contreras-Acuña, M; García-Barrera, T; García-Sevillano, M A; Gómez-Ariza, J L

2013-03-22

Arsenic species have been investigated in Anemonia sulcata, which is frequently consumed food staple in Spain battered in wheat flour and fried with olive oil. Speciation in tissue extracts was carried out by anion/cation exchange chromatography with inductively coupled plasma mass spectrometry (HPLC-(AEC/CEC)-ICP-MS). Three methods for the extraction of arsenic species were investigated (ultrasonic bath, ultrasonic probe and focused microwave) and the optimal one was applied. Arsenic speciation was carried out in raw and cooked anemone and the dominant species are dimethylarsinic acid (DMA(V)) followed by arsenobetaine (AB), As(V), monomethylarsonic acid (MA(V)), tetramethylarsonium ion (TETRA) and trimethylarsine oxide (TMAO). In addition, arsenocholine (AsC), glyceryl phosphorylarsenocholine (GPAsC) and dimethylarsinothioic acid (DMAS) were identified by liquid chromatography coupled to triple quadrupole mass spectrometry (HPLC-MS). These results are interesting since GPAsC has been previously reported in marine organisms after experimental exposure to AsC, but not in natural samples. In addition, this paper reports for the first time the identification of DMAS in marine food. Copyright © 2013 Elsevier B.V. All rights reserved.

Assessment of occupational exposure to inorganic arsenic based on urinary concentrations and speciation of arsenic.

PubMed Central

Farmer, J G; Johnson, L R

1990-01-01

An analytical speciation method, capable of separating inorganic arsenic (As (V), As (III] and its methylated metabolites (MMAA, DMAA) from common, inert, dietary organoarsenicals, was applied to the determination of arsenic in urine from a variety of workers occupationally exposed to inorganic arsenic compounds. Mean urinary arsenic (As (V) + As (III) + MMAA + DMAA) concentrations ranged from 4.4 micrograms/g creatinine for controls to less than 10 micrograms/g for those in the electronics industry, 47.9 micrograms/g for timber treatment workers applying arsenical wood preservatives, 79.4 micrograms/g for a group of glassworkers using arsenic trioxide, and 245 micrograms/g for chemical workers engaged in manufacturing and handling inorganic arsenicals. The maximum recorded concentration was 956 micrograms/g. For the most exposed groups, the ranges in the average urinary arsenic speciation pattern were 1-6% As (V), 11-14% As (III), 14-18% MMAA, and 63-70% DMAA. The highly raised urinary arsenic concentrations for the chemical workers, in particular, and some glassworkers are shown to correspond to possible atmospheric concentrations in the workplace and intakes in excess of, or close to, recommended and statutory limits and those associated with inorganic arsenic related diseases. PMID:2357455

Concentrations and speciation of heavy metals in sludge from nine textile dyeing plants.

PubMed

Liang, Xin; Ning, Xun-an; Chen, Guoxin; Lin, Meiqing; Liu, Jingyong; Wang, Yujie

2013-12-01

The safe disposal of sludge from textile dyeing industry requires research on bioavailability and concentration of heavy metals. In this study, concentrations and chemical speciation of heavy metals (Cd, Cr, Cu, Ni, Zn, Pb) in sludge from nine different textile dyeing plants were examined. Some physiochemical features of sludge from textile dyeing industry were determined, and a sequential extraction procedure recommended by the Community Bureau of Reference (BCR) was used to study the metal speciation. Cluster analysis (CA) and principal component analysis (PCA) were applied to provide additional information regarding differences in sludge composition. The results showed that Zn and Cu contents were the highest, followed by Ni, Cr, Cd and Pb. The concentration of Cd and Ni in some sludge samples exceeded the standard suggested for acidic soils in China (GB18918-2002). In sludge from textile dyeing plants, Pb, Cd and Cr were principally distributed in the oxidizable and residual fraction, Cu in the oxidizable fraction, Ni in all four fractions and Zn in the acid soluble/exchangeable and reducible fractions. The pH and heat-drying method affected the fractionation of heavy metals in sludge. © 2013 Elsevier Inc. All rights reserved.

Profiling planktonic biomass using element-specific, multicomponent nuclear magnetic resonance spectroscopy.

PubMed

Komatsu, Takanori; Kobayashi, Toshiya; Hatanaka, Minoru; Kikuchi, Jun

2015-06-02

Planktonic metabolism plays crucial roles in Earth's elemental cycles. Chemical speciation as well as elemental stoichiometry is important for advancing our understanding of planktonic roles in biogeochemical cycles. In this study, a multicomponent solid-state nuclear magnetic resonance (NMR) approach is proposed for chemical speciation of cellular components, using several advanced NMR techniques. Measurements by ssNMR were performed on (13)C and (15)N-labeled Euglena gracilis, a flagellated protist. 3D dipolar-assisted rotational resonance, double-cross-polarization (1)H-(13)C correlation spectroscopy, and (1)H-(13)C solid-state heteronuclear single quantum correlation spectroscopy successively allowed characterization of cellular components. These techniques were then applied to E. gracilis cultured in high and low ammonium media to demonstrate the power of this method for profiling and comparing cellular components. Cellular NMR spectra indicated that ammonium induced both paramylon degradation and amination. Arginine was stored as a nitrogen reserve and ammonium replaced by arginine catabolism via the arginine dihydrolase pathway. (15)N and (31)P cellular ssNMR indicated arginine and polyphosphate accumulation in E. gracilis, respectively. This chemical speciation technique will contribute to environmental research by providing detailed information on environmental chemical properties.

Soft X-ray spectromicroscopy for speciation, quantitation and nano-eco-toxicology of nanomaterials.

PubMed

Lawrence, J R; Swerhone, G D W; Dynes, J J; Korber, D R; Hitchcock, A P

2016-02-01

There is a critical need for methods that provide simultaneous detection, identification, quantitation and visualization of nanomaterials at their interface with biological and environmental systems. The approach should allow speciation as well as elemental analysis. Using the intrinsic X-ray absorption properties, soft X-ray scanning transmission X-ray spectromicroscopy (STXM) allows characterization and imaging of a broad range of nanomaterials, including metals, oxides and organic materials, and at the same time is able to provide detailed mapping of biological components. Thus, STXM offers considerable potential for application to research on nanomaterials in biology and the environment. The potential and limitations of STXM in this context are discussed using a range of examples, focusing on the interaction of nanomaterials with microbial cells, biofilms and extracellular polymers. The studies outlined include speciation and mapping of metal-containing nanomaterials (Ti, Ni, Cu) and carbon-based nanomaterials (multiwalled carbon nanotubes, C60 fullerene). The benefits of X-ray fluorescence detection in soft X-ray STXM are illustrated with a study of low levels of Ni in a natural river biofilm. © 2014 The Authors Journal of Microscopy © 2014 Royal Microscopical Society.

Not a simple case - A first comprehensive phylogenetic hypothesis for the Midas cichlid complex in Nicaragua (Teleostei: Cichlidae: Amphilophus).

PubMed

Geiger, Matthias F; McCrary, Jeffrey K; Schliewen, Ulrich K

2010-09-01

Nicaraguan Midas cichlids from crater lakes have recently attracted attention as potential model systems for speciation research, but no attempt has been made to comprehensively reconstruct phylogenetic relationships of this highly diverse and recently evolved species complex. We present a first AFLP (2793 loci) and mtDNA based phylogenetic hypothesis including all described and several undescribed species from six crater lakes (Apoyeque, Apoyo, Asososca Leon, Masaya, Tiscapa and Xiloá), the two great Lakes Managua and Nicaragua and the San Juan River. Our analyses demonstrate that the relationships between the Midas cichlid members are complex, and that phylogenetic information from different markers and methods do not always yield congruent results. Nevertheless, monophyly support for crater lake assemblages from Lakes Apoyeque, Apoyo, A. Leon is high as compared to those from L. Xiloá indicating occurrence of sympatric speciation. Further, we demonstrate that a 'three species' concept for the Midas cichlid complex is inapplicable and consequently that an individualized and voucher based approach in speciation research of the Midas cichlid complex is necessary at least as long as there is no comprehensive revision of the species complex available. Copyright 2010 Elsevier Inc. All rights reserved.

The shape and temporal dynamics of phylogenetic trees arising from geographic speciation.

PubMed

Pigot, Alex L; Phillimore, Albert B; Owens, Ian P F; Orme, C David L

2010-12-01

Phylogenetic trees often depart from the expectations of stochastic models, exhibiting imbalance in diversification among lineages and slowdowns in the rate of lineage accumulation through time. Such departures have led to a widespread perception that ecological differences among species or adaptation and subsequent niche filling are required to explain patterns of diversification. However, a key element missing from models of diversification is the geographical context of speciation and extinction. In this study, we develop a spatially explicit model of geographic range evolution and cladogenesis, where speciation arises via vicariance or peripatry, and explore the effects of these processes on patterns of diversification. We compare the results with those observed in 41 reconstructed avian trees. Our model shows that nonconstant rates of speciation and extinction are emergent properties of the apportioning of geographic ranges that accompanies speciation. The dynamics of diversification exhibit wide variation, depending on the mode of speciation, tendency for range expansion, and rate of range evolution. By varying these parameters, the model is able to capture many, but not all, of the features exhibited by birth-death trees and extant bird clades. Under scenarios with relatively stable geographic ranges, strong slowdowns in diversification rates are produced, with faster rates of range dynamics leading to constant or accelerating rates of apparent diversification. A peripatric model of speciation with stable ranges also generates highly unbalanced trees typical of bird phylogenies but fails to produce realistic range size distributions among the extant species. Results most similar to those of a birth-death process are reached under a peripatric speciation scenario with highly volatile range dynamics. Taken together, our results demonstrate that considering the geographical context of speciation and extinction provides a more conservative null model of diversification and offers a very different perspective on the phylogenetic patterns expected in the absence of ecology.

Biological signatures of dynamic river networks from a coupled landscape evolution and neutral community model

NASA Astrophysics Data System (ADS)

Stokes, M.; Perron, J. T.

2017-12-01

Freshwater systems host exceptionally species-rich communities whose spatial structure is dictated by the topology of the river networks they inhabit. Over geologic time, river networks are dynamic; drainage basins shrink and grow, and river capture establishes new connections between previously separated regions. It has been hypothesized that these changes in river network structure influence the evolution of life by exchanging and isolating species, perhaps boosting biodiversity in the process. However, no general model exists to predict the evolutionary consequences of landscape change. We couple a neutral community model of freshwater organisms to a landscape evolution model in which the river network undergoes drainage divide migration and repeated river capture. Neutral community models are macro-ecological models that include stochastic speciation and dispersal to produce realistic patterns of biodiversity. We explore the consequences of three modes of speciation - point mutation, time-protracted, and vicariant (geographic) speciation - by tracking patterns of diversity in time and comparing the final result to an equilibrium solution of the neutral model on the final landscape. Under point mutation, a simple model of stochastic and instantaneous speciation, the results are identical to the equilibrium solution and indicate the dominance of the species-area relationship in forming patterns of diversity. The number of species in a basin is proportional to its area, and regional species richness reaches its maximum when drainage area is evenly distributed among sub-basins. Time-protracted speciation is also modeled as a stochastic process, but in order to produce more realistic rates of diversification, speciation is not assumed to be instantaneous. Rather, each new species must persist for a certain amount of time before it is considered to be established. When vicariance (geographic speciation) is included, there is a transient signature of increased regional diversity after river capture. The results indicate that the mode of speciation and the rate of speciation relative to the rate of divide migration determine the evolutionary signature of river capture.

Speciation gradients and the distribution of biodiversity.

PubMed

Schluter, Dolph; Pennell, Matthew W

2017-05-31

Global patterns of biodiversity are influenced by spatial and environmental variations in the rate at which new species form. We relate variations in speciation rates to six key patterns of biodiversity worldwide, including the species-area relationship, latitudinal gradients in species and genetic diversity, and between-habitat differences in species richness. Although they sometimes mirror biodiversity patterns, recent rates of speciation, at the tip of the tree of life, are often highest where species richness is low. Speciation gradients therefore shape, but are also shaped by, biodiversity gradients and are often more useful for predicting future patterns of biodiversity than for interpreting the past.

Determination and pharmacokinetic properties of arsenic speciation in Xiao-Er-Zhi-Bao-Wan by high-performance liquid chromatography with inductively coupled plasma mass spectrometry.

PubMed

Han, Xu; Luo, Jiaoyang; Zhou, Wenju; Yang, Shihai; Yang, Meihua

2016-10-01

A method of high performance liquid chromatography with a Hamilton PRP-X100 ion-exchange column (250 × 4.1 mm id, 10 μm) coupled to inductively coupled plasma mass spectrometry was employed to generate a full concentration-time profile of arsenic speciation after oral administration. The results exhibited good linearity and revealed that, in the pills, the average arsenic concentration was 10105.4 ± 380.7 mg/kg, and in the water extraction solution, the inorganic As(III) and As(V) concentrations were 220.1 ± 12.6 and 45.5 ± 2.3 mg/kg, respectively. No trace of monomethyl arsenic acid was detected in any of the plasma samples. We then successfully applied the established methodology to examine the pharmacokinetics of arsenic speciation. The resulting data revealed that, after oral administration in rats, the plasma concentration of each arsenic species reached C max shortly after initial dosing, and that the distribution and elimination of As(V) was faster than that of As(III) and dimethyl arsenic acid. Additionally, the t 1/2 values of As(V), As(III), and dimethyl arsenic acid were 3.4 ± 1.6, 14.3 ± 4.0, and 19.9 ± 1.6 h, respectively. This study provides references for the determination of arsenic speciation in mineral-containing medicines and could serve as a useful tool in measuring the true toxicity in traditional medicines that contain them. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The variability in iron speciation in size fractionated residual oil fly ash particulate matter (ROFA PM).

PubMed

Pattanaik, Sidhartha; Huggins, Frank E; Huffman, Gerald P

2016-08-15

Ambient particulate matter (PM) containing iron can catalyze Fenton reaction leading to the production of reactive oxygen species in cells. It can also catalyze atmospheric redox reaction. These reactions are governed by the physicochemical characteristics of iron in ambient PM. As a surrogate for ambient PM, we prepared residual oil fly ash PM (ROFA PM) in a practical fire tube boiler firing residual oils with varying sulfur and ash contents. The ROFA particles were resolved into fine PM or PM2.5 (aerodynamic diameter (AD)<2.5μm) and coarse PM or PM2.5+ (AD between 2.5μm and 50μm). The iron speciation in PM2.5+ was ascertained using X-ray absorption spectroscopy and leaching method while that in PM2.5 was reported earlier. The results of both studies are compared to get an insight into the variability in the iron speciation in different size fractions. The results show the predominance of ferric sulfate, with a minor spinal ferrite in both PM (i.e. ZnxNi1-xFe2O4 in PM2.5, ZnFe2O4 in PM2.5+). The iron solubility in ROFA PM depends on its speciation, mode of incorporation of iron into particle's carbonaceous matrix, the grade and composition of oils, and pH of the medium. The soluble fraction of iron in PM is critical in assessing its interaction with the biological systems and its toxic potential. Copyright © 2016 Elsevier B.V. All rights reserved.

Selective speciation improves efficacy and lowers toxicity of platinum anticancer and vanadium antidiabetic drugs.

PubMed

Doucette, Kaitlin A; Hassell, Kelly N; Crans, Debbie C

2016-12-01

Improving efficacy and lowering resistance to metal-based drugs can be addressed by consideration of the coordination complex speciation and key reactions important to vanadium antidiabetic drugs or platinum anticancer drugs under biological conditions. The methods of analyses vary depending on the specific metal ion chemistry. The vanadium compounds interconvert readily, whereas the reactions of the platinum compounds are much slower and thus much easier to study. However, the vanadium species are readily differentiated due to vanadium complexes differing in color. For both vanadium and platinum systems, understanding the processes as the compounds, Lipoplatin and Satraplatin, enter cells is needed to better combat the disease; there are many cellular metabolites, which may affect processing and thus the efficacy of the drugs. Examples of two formulations of platinum compounds illustrate how changing the chemistry of the platinum will result in less toxic and better tolerated drugs. The consequence of the much lower toxicity of the drug, can be readily realized because cisplatin administration requires hospital stay whereas Lipoplatin can be done in an outpatient manner. Similarly, the properties of Satraplatin allow for development of an oral drug. These forms of platinum demonstrate that the direct consequence of more selective speciation is lower side effects and cheaper administration of the anticancer agent. Therefore we urge that as the community goes forward in development of new drugs, control of speciation chemistry will be considered as one of the key strategies in the future development of anticancer drugs. Copyright © 2016 Elsevier Inc. All rights reserved.

Evaluation of mercury speciation and removal through air pollution control devices of a 190 MW boiler.

PubMed

Wu, Chengli; Cao, Yan; Dong, Zhongbing; Cheng, Chinmin; Li, Hanxu; Pan, Weiping

2010-01-01

Air pollution control devices (APCDs) are installed at coal-fired power plants for air pollutant regulation. Selective catalytic reduction (SCR) and wet flue gas desulfurization (FGD) systems have the co-benefits of air pollutant and mercury removal. Configuration and operational conditions of APCDs and mercury speciation affect mercury removal efficiently at coal-fired utilities. The Ontario Hydro Method (OHM) recommended by the U.S. Environmental Protection Agency (EPA) was used to determine mercury speciation simultaneously at five sampling locations through SCR-ESP-FGD at a 190 MW unit. Chlorine in coal had been suggested as a factor affecting the mercury speciation in flue gas; and low-chlorine coal was purported to produce less oxidized mercury (Hg2+) and more elemental mercury (Hg0) at the SCR inlet compared to higher chlorine coal. SCR could oxidize elemental mercury into oxidized mercury when SCR was in service, and oxidation efficiency reached 71.0%. Therefore, oxidized mercury removal efficiency was enhanced through a wet FGD system. In the non-ozone season, about 89.5%-96.8% of oxidized mercury was controlled, but only 54.9%-68.8% of the total mercury was captured through wet FGD. Oxidized mercury removal efficiency was 95.9%-98.0%, and there was a big difference in the total mercury removal efficiencies from 78.0% to 90.2% in the ozone season. Mercury mass balance was evaluated to validate reliability of OHM testing data, and the ratio of mercury input in the coal to mercury output at the stack was from 0.84 to 1.08.

[Treatment of tannery wastewater by infiltration percolation: chromium removal and speciation in soil].

PubMed

Tiglyene, S; Jaouad, A; Mandi, L

2008-06-01

The aim of this paper was, on one hand, to study the treatment of raw tannery effluent by infiltration percolation system and, on the other hand, to determine the distribution and speciation of chromium in the used soil. The system pilot consisted of columns filled to 15 cm of gravel and 60 cm of soil (88% of sand). The columns irrigated by raw tannery wastewater with a daily hydraulic load of 5 cm per day (approximately 10 L every day). The water flowed vertically through the soil. The speciation of Cr was investigated by using selective five steps sequential extraction method. The results indicated that the pH of the treated wastewater increases by three units in comparison to the raw wastewater. The electrical conductivity of the effluent increases also after treatment. Over the whole experimental period, results revealed significant performances of infiltration percolation system for organic load reduction. The mean elimination rate was 74% for total COD. In addition, there was a significant accumulation of organic carbon (62%) in the surface strata for the system. The total chromium undergoes an overall removal of 98%. After seven months of experiment, the results indicated that the whole retention of Cr occurring in the surface horizon of the soil (69%). Furthermore, the speciation study of Cr in the soil revealed that the oxidizable fraction is the most represented 55%. The reducible and residual phases represent 17.5% and 18.5%, respectively. The carbonate fraction presented 9% while exchangeable fraction presented only 0.02%.

[Effects of Low-Molecular-Weight Organic Acids on the Speciation of Pb in Purple Soil and Soil Solution].

PubMed

Liu, Jiang; Jiang, Tao; Huang, Rong; Zhang, Jin-zhong; Chen, Hong

2016-04-15

Lead (Pb) in purple soil was selected as the research target, using one-step extraction method with 0.01 mol · L⁻¹ sodium nitrate as the background electrolyte to study the release effect of citric acid (CA), tartaric acid (TA) and acetic acid (AC) with different concentrations. Sequential extraction and geochemical model (Visual Minteq v3.0) were applied to analyze and predict the speciation of Pb in soil solid phase and soil solution phase. Then the ebvironmental implications and risks of low-molecule weight organic acid (LMWOA) on soil Pb were analyzed. The results indicated that all three types of LMWOA increased the desorption capacity of Pb in purple soil, and the effect followed the descending order of CA > TA > AC. After the action of LMWOAs, the exchangeable Pb increased; the carbonate-bound Pb and Fe-Mn oxide bound Pb dropped in soil solid phase. Organic bound Pb was the main speciation in soil solution phase, accounting for 45.16%-75.05%. The following speciation of Pb in soil solution was free Pb, accounting for 22.71%-50.25%. For CA and TA treatments, free Pb ions and inorganic bound Pb in soil solution increased with increasing LMWOAs concentration, while organic bound Pb suffered a decrease in this process. An opposite trend for AC treatment was observed compared with CA and TA treatments. Overall, LMWOAs boosted the bioavailability of Pb in purple soil and had a potential risk to contaminate underground water. Among the three LMWOAs in this study, CA had the largest potential to activate soil Pb.

New mitochondrial DNA data affirm the importance of Pleistocene speciation in North American birds.

PubMed

Johnson, Ned K; Cicero, Carla

2004-05-01

The timing of origin of modern North American bird species in relation to Pleistocene glaciations has long been the topic of significant discussion and disagreement. Recently, Klicka and Zink (1997) and Avise and Walker (1998) enlivened this debate by using calibrated molecular distance values to estimate timing of speciations. Here we use new molecular studies to test their conclusions. Molecular distance values for 39 pairs of proven sister species, 27 of which are based on new data, alter the currently perceived pattern that avian species splits occurred mainly in the Pliocene and early-mid-Pleistocene. Mitochondrial DNA divergence values for this set of taxa showed a skewed distribution pointing toward relatively young speciation times, in contrast to the pattern presented by Klicka and Zink (1997) for 35 sister plus non-sister species pairs. Our pattern was not significantly different from that of Avise and Walker (1998) for "intraspecific phylogroups," some of which are species. We conclude that the entire Pleistocene, including the last two glacial cycles (<250,000 years ago), was important in speciations of modern North American birds. A substantial number of speciations were both initiated and completed in the last 250,000 years. Simultaneously, many taxa began to diverge in the Pleistocene but their speciations are not yet complete (per Avise and Walker 1998). The suggestion that durations of speciations average two million years is probably a substantial overestimate.

Ecological Impacts of Reverse Speciation in Threespine Stickleback.

PubMed

Rudman, Seth M; Schluter, Dolph

2016-02-22

Young species are highly prone to extinction via increased gene flow after human-caused environmental changes. This mechanism of biodiversity loss, often termed reverse speciation or introgressive extinction, is of exceptional interest because the parent species are typically highly differentiated ecologically. Reverse speciation events are potentially powerful case studies for the role of evolution in driving ecological changes, as the phenotypic shifts associated with introgressive extinction can be large and they occur over particularly short timescales. Furthermore, reverse speciation can lead to novel phenotypes, which may in turn produce novel ecological effects. Here we investigate the ecological shift associated with reverse speciation in threespine stickleback fish using a field study and a replicated experiment. We find that an instance of introgressive extinction had cascading ecological consequences that altered the abundance of both aquatic prey and the pupating aquatic insects that emerged into the terrestrial ecosystem. The community and ecosystem impacts of reverse speciation were novel, and yet they were also predictable based on ecological and morphological considerations. The study suggests that knowledge about the community ecology and changes in functional morphology of a dominant species may lead to some predictive power for the ecological effects of evolutionary change. Moreover, the rapid nature and resultant ecological impacts associated with reverse speciation demonstrates the interplay between biodiversity, evolutionary change, and ecosystem function. Copyright © 2016 Elsevier Ltd. All rights reserved.

Refining the conditions for sympatric ecological speciation.

PubMed

Débarre, F

2012-12-01

Can speciation occur in a single population when different types of resources are available, in the absence of any geographical isolation, or any spatial or temporal variation in selection? The controversial topics of sympatric speciation and ecological speciation have already stimulated many theoretical studies, most of them agreeing on the fact that mechanisms generating disruptive selection, some level of assortment, and enough heterogeneity in the available resources, are critical for sympatric speciation to occur. Few studies, however, have combined the three factors and investigated their interactions. In this article, I analytically derive conditions for sympatric speciation in a general model where the distribution of resources can be uni- or bimodal, and where a parameter controls the range of resources that an individual can exploit. This approach bridges the gap between models of a unimodal continuum of resources and Levene-type models with discrete resources. I then test these conditions against simulation results from a recently published article (Thibert-Plante & Hendry, 2011, J. Evol. Biol. 24: 2186-2196) and confirm that sympatric ecological speciation is favoured when (i) selection is disruptive (i.e. individuals with an intermediate trait are at a local fitness minimum), (ii) resources are differentiated enough and (iii) mating is assortative. I also discuss the role of mating preference functions and the need (or lack thereof) for bimodality in resource distributions for diversification. © 2012 The Author. Journal of Evolutionary Biology © 2012 European Society For Evolutionary Biology.

METHODS TO CLASSIFY ENVIRONMENTAL SAMPLES BASED ON MOLD ANALYSES BY QPCR

EPA Science Inventory

Quantitative PCR (QPCR) analysis of molds in indoor environmental samples produces highly accurate speciation and enumeration data. In a number of studies, eighty of the most common or potentially problematic indoor molds were identified and quantified in dust samples from homes...

ISSUES RELATED TO SOLUTION CHEMISTRY IN MERCURY SAMPLING IMPINGERS

EPA Science Inventory

Analysis of mercury (Hg) speciation in combustion flue gases is often accomplished in standardized sampling trains in which the sample is passed sequentially through a series of aqueous solutions to capture and separate oxidized Hg (Hg2+) and elemental Hg (Hgo). Such methods incl...

STANDARDIZED AUTOMATED AND MANUAL METHODS TO SPECIATE MERCURY: FIELD AND LABORATORY STUDIES

EPA Science Inventory

The urban atmosphere contains a large number of air pollutants including mercury. Atmospheric mercury is predominantly present in the elemental form (Hg0). However emissions from industrial activities (e.g. incinerators, fossil fuel combustion sources and others) emit other f...

Reversed Phase Column HPLC-ICP-MS Conditions for Arsenic Speciation Analysis of Rice Flour.

PubMed

Narukawa, Tomohiro; Matsumoto, Eri; Nishimura, Tsutomu; Hioki, Akiharu

2015-01-01

New measurement conditions for arsenic speciation analysis of rice flour were developed using HPLC-ICP-MS equipped with a reversed phase ODS column. Eight arsenic species, namely, arsenite [As(III)], arsenate [As(V)], monomethylarsonic acid (MMAA), dimethylarsinic acid (DMAA), trimethylarsine oxide (TMAO), tetramethylarsonium (TeMA), arsenobetaine (AsB) and arsenocholine (AsC), were separated and determined under the proposed conditions. In particular, As(III) and MMAA and DMAA and AsB were completely separated using a newly proposed eluent containing ammonium dihydrogen phosphate. Importantly, the sensitivity changes, in particular those of As(V) and As(III) caused by coexisting elements and by complex matrix composition, which had been problematical in previously reported methods, were eliminated. The new eluent can be applied to C8, C18 and C30 ODS columns with the same effectiveness and with excellent repeatability. The proposed analytical method was successfully applied to extracts of rice flour certified reference materials.

Anagenesis, Cladogenesis, and Speciation on Islands.

PubMed

Emerson, Brent C; Patiño, Jairo

2018-05-03

Anagenesis and cladogenesis are fundamental evolutionary concepts, but are increasingly being adopted as speciation models in the field of island biogeography. Here, we review the origin of the terms 'anagenetic' and 'cladogenetic' speciation, critique their utility, and finally suggest alternative terminology that better describes the geographical relationships of insular sister species. Copyright © 2018 Elsevier Ltd. All rights reserved.

Experimental Studies of Phase Equilibria of Meteorites and Planetary Bodies

NASA Technical Reports Server (NTRS)

Stolper, Edward M.

2005-01-01

The primary theme of this project was the application of experimental petrology and geochemistry to a variety of problems in meteoritics and planetary geology. The studies were designed to help develop constraints on the histories of primitive meteorites and their components, the environments in which they formed and evolved, and to understand quantitatively the processes involved in the evolution of igneous rocks on the earth and other planetary bodies. We undertook several projects relating to the origin of CAIs and chondrules. Systematics in the thermodynamic properties of CAI-like liquids were investigated and used to elucidate speciation of multi-valent cations and sulfide capacity of silicate melts and to constrain redox conditions and the vapor pressures of volatile species over molten chondrules. We experimentally determined vanadium speciation in meteoritic pyroxenes and in pyroxenes crystallized from CAI-like melts under very reducing conditions. We also found that bulk oxygen isotope compositions of chondrules in the moderately unequilibrated LL chondrites are related to the relative timing of plagioclase crystallization. We completed an experimental study on the vaporization of beta-SiC and SiO2 (glass or cristobalite) in reducing gases and established the conditions under which these presolar grains could have survived in the solar nebula. We expanded our technique for determining the thermodynamic properties of minerals and liquids to iron-bearing systems. We determined activity-composition relationships in Pt-Fe, Pt-Cr and Pt-Fe-Cr alloys. Results were used to determine the thermodynamic properties of chromite-picrochromite spinels including the free energy of formation of end-member FeCr2O4. We also established a new approach for evaluating Pt-Fe saturation experiments. We calculated the T-fO2 relationships in equilibrated ordinary chondrites and thereby constrained the conditions of metamorphism in their parent bodies.

Predicting Soluble Nickel in Soils Using Soil Properties and Total Nickel

PubMed Central

Zhang, Xiaoqing; Li, Jumei; Wei, Dongpu; Li, Bo; Ma, Yibing

2015-01-01

Soil soluble nickel (Ni) concentration is very important for determining soil Ni toxicity. In the present study, the relationships between soil properties, total and soluble Ni concentrations in soils were developed in a wide range of soils with different properties and climate characteristics. The multiple regressions showed that soil pH and total soil Ni concentrations were the most significant parameters in predicting soluble Ni concentrations with the adjusted determination coefficients (Radj 2) values of 0.75 and 0.68 for soils spiked with soluble Ni salt and the spiked soils leached with artificial rainwater to mimic field conditions, respectively. However, when the soils were divided into three categories (pH < 7, 7–8 and > 8), they obtained better predictions with Radj 2 values of 0.78–0.90 and 0.79–0.94 for leached and unleached soils, respectively. Meanwhile, the other soil properties, such as amorphous Fe and Al oxides and clay, were also found to be important for determining soluble Ni concentrations, indicating that they were also presented as active adsorbent surfaces. Additionally, the whole soil speciation including bulk soil properties and total soils Ni concentrations were analyzed by mechanistic speciation models WHAM VI and Visual MINTEQ3.0. It was found that WHAM VI provided the best predictions for the soils with pH < 7, was relatively reasonable for pH 7 to 8, and gave an overestimation for pH > 8. The Visual MINTEQ3.0 could provide better estimation for pH < 8 and meanwhile quite reasonable results for pH > 8. These results indicated the possibility and applicability of these models to predict soil soluble Ni concentration by soil properties. PMID:26217951

Predicting Soluble Nickel in Soils Using Soil Properties and Total Nickel.

PubMed

Zhang, Xiaoqing; Li, Jumei; Wei, Dongpu; Li, Bo; Ma, Yibing

2015-01-01

Soil soluble nickel (Ni) concentration is very important for determining soil Ni toxicity. In the present study, the relationships between soil properties, total and soluble Ni concentrations in soils were developed in a wide range of soils with different properties and climate characteristics. The multiple regressions showed that soil pH and total soil Ni concentrations were the most significant parameters in predicting soluble Ni concentrations with the adjusted determination coefficients (Radj2) values of 0.75 and 0.68 for soils spiked with soluble Ni salt and the spiked soils leached with artificial rainwater to mimic field conditions, respectively. However, when the soils were divided into three categories (pH < 7, 7-8 and > 8), they obtained better predictions with Radj2 values of 0.78-0.90 and 0.79-0.94 for leached and unleached soils, respectively. Meanwhile, the other soil properties, such as amorphous Fe and Al oxides and clay, were also found to be important for determining soluble Ni concentrations, indicating that they were also presented as active adsorbent surfaces. Additionally, the whole soil speciation including bulk soil properties and total soils Ni concentrations were analyzed by mechanistic speciation models WHAM VI and Visual MINTEQ3.0. It was found that WHAM VI provided the best predictions for the soils with pH < 7, was relatively reasonable for pH 7 to 8, and gave an overestimation for pH > 8. The Visual MINTEQ3.0 could provide better estimation for pH < 8 and meanwhile quite reasonable results for pH > 8. These results indicated the possibility and applicability of these models to predict soil soluble Ni concentration by soil properties.

Speciation of arsenic in pyrite by micro-X-ray absorption fine- structure spectroscopy (XAFS)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paktunc, D.

2008-09-30

Pyrite (FeS2) often contains variable levels of arsenic, regardless of the environment of formation. Arsenian pyrite has been reported in coals, sediments and ore deposits. Arsenian pyrite having As concentrations of up to 10 wt % in sedimentary rocks (Kolker et al. 1997), about 10 wt% in gold deposits (Fleet et al. 1993), 12 wt % in a refractory gold ore (Paktunc et al. 2006) and 20 wt % in a Carlin-type gold deposit in Nevada (Reich et al. 2005) have been reported. Arsenian pyrite is the carrier of gold in hydrothermal Carlin-type gold deposits, and gold concentrations of upmore » to 0.9 wt % have been reported (Reich et al. 2005; Paktunc et al. 2006). In general, high Au concentrations correlate with As-rich zones in pyrite (Paktunc et al. 2006). Pyrite often ends up in mining and metallurgical wastes as an unwanted mineral and consititutes one of the primary sources of As in the wastes. Arsenic can be readily released to the environment due to rapid oxidative dissolution of host pyrite under atmospheric conditions. Pyrite is also the primary source of arsenic in emissions and dust resulting from combustion of bituminous coals. Despite the importance of arsenian pyrite as a primary source of anthropogenic arsenic in the environment and its economic significance as the primary carrier of gold in Carlin-type gold deposits, our understanding of the nature of arsenic in pyrite is limited. There are few papers dealing with the mode of occurrence of arsenic by bulk XAFS in a limited number of pyrite-bearing samples. The present study documents the analysis of pyrite particles displaying different morphologies and a range of arsenic and gold concentrations to determine the nature and speciation of arsenic.« less

Arsenic and chromium speciation in an urban contaminated soil.

PubMed

Landrot, Gautier; Tappero, Ryan; Webb, Samuel M; Sparks, Donald L

2012-08-01

The distribution and speciation of As and Cr in a contaminated soil were studied by synchrotron-based X-ray microfluorescence (μ-XRF), microfocused X-ray absorption spectroscopy (μ-XAS), and bulk extended X-ray absorption fine structure spectroscopy (EXAFS). The soil was taken from a park in Wilmington, DE, which had been an important center for the leather tanning industry along the Atlantic seaboard of the United States, until the early 20th century. Soil concentrations of As, Cr, and Pb measured at certain locations in the park greatly exceeded the background levels of these heavy metals in the State of Delaware. Results show that Cr(III) and As(V) species are mainly present in the soil, with insignificant amounts of Cr(VI) and As(III). Micro-XRF maps show that Cr and Fe are distributed together in regions where their concentrations are diffuse, and at local spots where their concentrations are high. Iron oxides, which can reduce Cr(VI) to Cr(III), are present at some of these hot spots where Cr and Fe are highly concentrated. Arsenic is mainly associated with Al in the soil, and to a minor extent with Fe. Arsenate may be sorbed to aluminum oxides, which might have transformed after a long period of time into an As-Al precipitate phase, having a structure and chemical composition similar to mansfieldite (AlAsO(4)⋅2H(2)O). The latter hypothesis is supported by the fact that only a small amount of As present in the soil was desorbed using the characteristic toxicity leaching procedure tests. This suggests that As is immobilized in the soil. Copyright © 2012 Elsevier Ltd. All rights reserved.

Evolutionary analysis of Old World arenaviruses reveals a major adaptive contribution of the viral polymerase.

PubMed

Pontremoli, Chiara; Forni, Diego; Cagliani, Rachele; Pozzoli, Uberto; Riva, Stefania; Bravo, Ignacio G; Clerici, Mario; Sironi, Manuela

2017-10-01

The Old World (OW) arenavirus complex includes several species of rodent-borne viruses, some of which (i.e., Lassa virus, LASV and Lymphocytic choriomeningitis virus, LCMV) cause human diseases. Most LCMV and LASV infections are caused by rodent-to-human transmissions. Thus, viral evolution is largely determined by events that occur in the wildlife reservoirs. We used a set of human- and rodent-derived viral sequences to investigate the evolutionary history underlying OW arenavirus speciation, as well as the more recent selective events that accompanied LASV spread in West Africa. We show that the viral RNA polymerase (L protein) was a major positive selection target in OW arenaviruses and during LASV out-of-Nigeria migration. No evidence of selection was observed for the glycoprotein, whereas positive selection acted on the nucleoprotein (NP) during LCMV speciation. Positively selected sites in L and NP are surrounded by highly conserved residues, and the bulk of the viral genome evolves under purifying selection. Several positively selected sites are likely to modulate viral replication/transcription. In both L and NP, structural features (solvent exposed surface area) are important determinants of site-wise evolutionary rate variation. By incorporating several rodent-derived sequences, we also performed an analysis of OW arenavirus codon adaptation to the human host. Results do not support a previously hypothesized role of codon adaptation in disease severity for non-Nigerian strains. In conclusion, L and NP represent the major selection targets and possible determinants of disease presentation; these results suggest that field surveys and experimental studies should primarily focus on these proteins. © 2017 John Wiley & Sons Ltd.

Formation, Evaporation, and Hydrolysis of Organic Nitrates from Nitrate Radical Oxidation of Monoterpenes

NASA Astrophysics Data System (ADS)

Ng, N. L.; Takeuchi, M.; Eris, G.; Berkemeier, T.; Boyd, C.; Nah, T.; Xu, L.

2017-12-01

Organic nitrates play an important role in the cycling of NOx and secondary organic aerosol (SOA) formation, yet their formation mechanisms and fates remain highly uncertain. The interactions of biogenic VOCs with NO3 radicals represent a direct way for positively linking anthropogenic and biogenic emissions. Results from ambient studies suggest that organic nitrates have a relatively short lifetime, though corresponding laboratory data are limited. SOA and organic nitrates produced at night may evaporate the following morning due to increasing temperatures or dilution of semi-volatile compounds. Once formed, organic nitrates can also undergo hydrolysis in the presence of particle water. In this work, we investigate the formation, evaporation, and hydrolysis of organic nitrates generated from the nitrate radical oxidation of a-pinene, b-pinene, and limonene. Experiments are conducted in the Georgia Environmental Chamber facility (GTEC) under dry and humid conditions and different temperatures. Experiments are also designed to probe different peroxy radical pathways (RO2+HO2 vs RO2+NO3). Speciated gas-phase and particle-phase organic nitrates are continuously monitored by a Filter Inlet for Gases and AEROsols High Resolution Time-of-Flight Chemical Ionization Mass Spectrometer (FIGAERO-HR-ToF-CIMS). Bulk aerosol composition is measured by a High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS). A large suite of highly oxygenated gas- and particle-phase organic nitrates are formed rapidly. We find a resistance to aerosol evaporation when it is heated. The extent of organic nitrate hydrolysis in the humid experiments is evaluated. The dynamics of the speciated organic nitrates over the course of the experiments will also be discussed. Results from this chamber study provide fundamental data for understanding the dynamics of organic nitrate aerosols over its atmospheric lifetime.

Chromium in urban sediment particulates: an integrated micro-chemical and XANES study

NASA Astrophysics Data System (ADS)

Taylor, Kevin; Byrne, Patrick; Hudson-Edwards, Karen

2015-04-01

Chromium is generally common within the urban sediment cascade as a result of abundant industrial and transport-related sources. The risks that Cr-bearing particles pose to ecosystems and humans depend on the solid phase chemical speciation of Cr in the particles. In this study, we use bulk chemical digests, sequential chemical extraction analysis, electron microscopy, electron microprobe and microfocus XANES analysis to describe the solid-phase speciation of Cr in urban particulate matter from both aquatic sediment and road dust sediment (RDS) in Manchester, UK. Cr-bearing grains within RDS are predominantly iron oxide grains, commonly of goethite or haematite mineralogy, but Cr-bearing silicate glass grains are also present. Iron oxide glass grains most likely have sorbed Cr, and derive from the rusting of Cr-steel particles from vehicles. Electron microprobe analysis indicates concentrations of Cr up to 3200 μg/g in these grains, and XANES analysis indicates that Cr(III) is the dominant oxidation state, with some trace amounts of Cr(VI). Cr-bearing grains within aquatic sediments are dominated by alumino-silicate glass grains derived from industrial waste. These grains contain Cr-rich areas with up to 19% Cr2O3 and XANES analysis indicates that Cr is present as Cr(III). The dominance of Cr(III) in these urban particulate grains suggests limited bioavailability or toxicity. However, the presence within two markedly different grain types (iron oxides and silicate glasses) indicates that the long-term geochemical behaviour and environmental risk of RDS and the aquatic sediments studied are likely to be quite different. These findings highlight the importance of understanding sources of metal contaminants in urban environments and the geochemical processes that affect their transfer through the urban sediment cascade and the wider river basin.

Genetic structure and bio-climatic modeling support allopatric over parapatric speciation along a latitudinal gradient.

PubMed

Rossetto, Maurizio; Allen, Chris B; Thurlby, Katie A G; Weston, Peter H; Milner, Melita L

2012-08-20

Four of the five species of Telopea (Proteaceae) are distributed in a latitudinal replacement pattern on the south-eastern Australian mainland. In similar circumstances, a simple allopatric speciation model that identifies the origins of genetic isolation within temporal geographic separation is considered as the default model. However, secondary contact between differentiated lineages can result in similar distributional patterns to those arising from a process of parapatric speciation (where gene flow between lineages remains uninterrupted during differentiation). Our aim was to use the characteristic distributional patterns in Telopea to test whether it reflected the evolutionary models of allopatric or parapatric speciation. Using a combination of genetic evidence and environmental niche modelling, we focused on three main questions: do currently described geographic borders coincide with genetic and environmental boundaries; are there hybrid zones in areas of secondary contact between closely related species; did species distributions contract during the last glacial maximum resulting in distributional gaps even where overlap and hybridisation currently occur? Total genomic DNA was extracted from 619 individuals sampled from 36 populations representing the four species. Seven nuclear microsatellites (nSSR) and six chloroplast microsatellites (cpSSR) were amplified across all populations. Genetic structure and the signature of admixture in overlap zones was described using the Bayesian clustering methods implemented in STUCTURE and NewHybrids respectively. Relationships between chlorotypes were reconstructed as a median-joining network. Environmental niche models were produced for all species using environmental parameters from both the present day and the last glacial maximum (LGM).The nSSR loci amplified a total of 154 alleles, while data for the cpSSR loci produced a network of six chlorotypes. STRUCTURE revealed an optimum number of five clusters corresponding to the four recognised species with the additional division of T. speciosissima into populations north and south of the Shoalhaven River valley. Unexpectedly, the northern disjunct population of T. oreades grouped with T. mongaensis and was identified as a hybrid swarm by the Bayesian assignment test implemented in NewHybrids. Present day and LGM environmental niche models differed dramatically, suggesting that distributions of all species had repeatedly expanded and contracted in response to Pleistocene climatic oscillations and confirming strongly marked historical distributional gaps among taxes. Genetic structure and bio-climatic modeling results are more consistent with a history of allopatric speciation followed by repeated episodes of secondary contact and localised hybridisation, rather than with parapatric speciation. This study on Telopea shows that the evidence for temporal exclusion of gene flow can be found even outside obvious geographical contexts, and that it is possible to make significant progress towards excluding parapatric speciation as a contributing evolutionary process.

Inverted Resistance Measurements as a Method for Characterizing the Bulk and Surface Conductivities of Three-Dimensional Topological Insulators

NASA Astrophysics Data System (ADS)

Eo, Y. S.; Sun, K.; Kurdak, ć.; Kim, D.-J.; Fisk, Z.

2018-04-01

We introduce a resistance measurement method that is useful in characterizing materials with both surface and bulk conduction, such as three-dimensional topological insulators. The transport geometry for this resistance measurement configuration consists of one current lead as a closed loop that fully encloses the other current lead on the surface, and two voltage leads that are both placed outside the loop. We show that, in the limit where the transport is dominated by the surface conductivity of the material, the four-terminal resistance measured from such a transport geometry is proportional to σb/σs2, where σb and σs are the bulk and surface conductivities of the material, respectively. We call this type of measurement inverted resistance measurement, as the resistance scales inversely with the bulk resistivity. We discuss possible implementations of this method by performing numerical calculations on different geometries and introduce strategies to extract the bulk and surface conductivities. We also demonstrate inverted resistance measurements on SmB6 , a topological Kondo insulator, using both single-sided and coaxially aligned double-sided Corbino disk transport geometries. Using this method, we are able to measure the bulk conductivity, even at low temperatures, where the bulk conduction is much smaller than the surface conduction in this material.

Assessing when chromosomal rearrangements affect the dynamics of speciation: implications from computer simulations

PubMed Central

Feder, Jeffrey L.; Nosil, Patrik; Flaxman, Samuel M.

2014-01-01

Many hypotheses have been put forth to explain the origin and spread of inversions, and their significance for speciation. Several recent genic models have proposed that inversions promote speciation with gene flow due to the adaptive significance of the genes contained within them and because of the effects inversions have on suppressing recombination. However, the consequences of inversions for the dynamics of genome wide divergence across the speciation continuum remain unclear, an issue we examine here. We review a framework for the genomics of speciation involving the congealing of the genome into alternate adaptive states representing species (“genome wide congealing”). We then place inversions in this context as examples of how genetic hitchhiking can potentially hasten genome wide congealing. Specifically, we use simulation models to (i) examine the conditions under which inversions may speed genome congealing and (ii) quantify predicted magnitudes of these effects. Effects of inversions on promoting speciation were most common and pronounced when inversions were initially fixed between populations before secondary contact and adaptation involved many genes with small fitness effects. Further work is required on the role of underdominance and epistasis between a few loci of major effect within inversions. The results highlight five important aspects of the roles of inversions in speciation: (i) the geographic context of the origins and spread of inversions, (ii) the conditions under which inversions can facilitate divergence, (iii) the magnitude of that facilitation, (iv) the extent to which the buildup of divergence is likely to be biased within vs. outside of inversions, and (v) the dynamics of the appearance and disappearance of exceptional divergence within inversions. We conclude by discussing the empirical challenges in showing that inversions play a central role in facilitating speciation with gene flow. PMID:25206365

Ecological speciation in an island snail: evidence for the parallel evolution of a novel ecotype and maintenance by ecologically dependent postzygotic isolation.

PubMed

Stankowski, Sean

2013-05-01

Speciation is the process by which reproductive isolation evolves between populations. Two general models of speciation have been proposed: ecological speciation, where reproductive barriers evolve due to ecologically based divergent selection, and mutation-order speciation, where populations fix different mutations as they adapt to similar selection pressures. I evaluate these alternative models and determine the progress of speciation in a diverse group of land snails, genus Rhagada, inhabiting Rosemary Island. A recently derived keeled-flat morphotype occupies two isolated rocky hills, while globose-shelled snails inhabit the surrounding plains. The study of one hill reveals that they are separated by a narrow hybrid zone. As predicted by ecological speciation theory, there are local and landscape level associations between shell shape and habitat, and the morphological transition coincides with a narrow ecotone between the two distinct environments. Microsatellite DNA revealed a cline of hybrid index scores much wider than the morphological cline, further supporting the ecological maintenance of the morphotypes. The hybrid zone does not run through an area of low population density, as is expected for mutation-order hybrid zones, and there is a unimodal distribution of phenotypes at the centre, suggesting that there is little or no prezygotic isolation. Instead, these data suggest that the ecotypes are maintained by ecologically dependent postzygotic isolation (i.e. ecological selection against hybrids). Mitochondrial and Microsatellite DNA indicate that the keeled-flat form evolved recently, and without major historical disruptions to gene flow. The data also suggest that the two keeled-flat populations, inhabiting similar rocky hills, have evolved in parallel. These snails provide a complex example of ecological speciation in its early stages. © 2013 Blackwell Publishing Ltd.

Role of natural nanoparticles on the speciation of Ni in andosols of la Reunion

NASA Astrophysics Data System (ADS)

Levard, Clément; Doelsch, Emmanuel; Rose, Jérôme; Masion, Armand; Basile-Doelsch, Isabelle; Proux, Olivier; Hazemann, Jean-Louis; Borschneck, Daniel; Bottero, Jean-Yves

2009-08-01

Andosols on the island of Réunion have high nickel (Ni) concentrations due to the natural pedo-geochemical background. Enhanced knowledge of Ni speciation is necessary to predict the bioavailability and potential toxicity of this element. Ni speciation in these andosols, marked by the presence of high amounts of natural aluminosilicate nanoparticles, was investigated in two complementary systems: (i) In a soil sample—densimetric fractionation was first performed in order to separate the potential bearing phases, prior to Ni speciation characterization. (ii) In a synthetic sample—Ni reactivity with synthetic aluminosilicate nanoparticle analogs were studied. In both cases, Ni speciation was determined using X-ray absorption spectroscopy (XAS). The results revealed that Ni had the same local environment in both systems (natural and synthetic systems), and Ni was chemically linked to natural short-range ordered aluminosilicates or analogs. This complex represented about 75% of the total Ni in the studied soil.

Speciation analysis of inorganic arsenic by magnetic solid phase extraction on-line with inductively coupled mass spectrometry determination.

PubMed

Montoro Leal, P; Vereda Alonso, E; López Guerrero, M M; Cordero, M T Siles; Cano Pavón, J M; García de Torres, A

2018-07-01

Arsenic, one of the main environmental pollutants and potent natural poison, is a chemical element that is spread throughout the Earth's crust. It is well known that the toxicity of arsenic is highly dependent on its chemical forms. Generally, the inorganic species are more toxic than its organics forms, and As(III) is 60 times more toxic than As(V). In environmental waters, arsenic exists predominantly in two chemical forms: As(III) and As(V). In view of these facts, fast, sensitive, accurate and simple analytical methods for the speciation of inorganic arsenic in environmental waters are required. In this work, a new magnetic solid phase extraction with a hydride generation system was coupled on line with inductively coupled plasma mass spectrometry (MSPE-HG-ICP-MS). The new system was based on the retention of As(III) and As(V) in two knotted reactors filled with (Fe 3 O 4 ) magnetic nanoparticles functionalized with [1,5-bis (2-pyridyl) 3-sulfophenylmethylene] thiocarbonohydrazide (PSTH-MNPs). As(III) and total inorganic As were sequentially eluted in different reduction conditions. The concentration of As(V) was obtained by subtracting As(III) from total As. The system runs in a fully automated way and the method has proved to have a wide linear range and to be precise, sensitive and fast. The detection limits found were 2.7 and 3.2 ng/L for As(III) and total As, respectively; with relative standard deviations (RSDs) of 2.5% and 2.7% and a sample throughput of 14.4 h -1 . In order to validate the developed method, several certified reference samples of environmental waters including sea water, were analyzed and the determined values were in good agreement with the certified values. The proposed method was successfully applied to the speciation analysis of inorganic arsenic in well-water and sea water. Copyright © 2018 Elsevier B.V. All rights reserved.

Total arsenic determination and speciation in infant food products by ion chromatography-inductively coupled plasma-mass spectrometry.

PubMed

Vela, Nohora P; Heitkemper, Douglas T

2004-01-01

Health risk associated with dietary arsenic intake may be different for infants and adults. Seafood is the main contributor to arsenic intake for adults while terrestrial-based food is the primary source for infants. Processed infant food products such as rice-based cereals, mixed rice/formula cereals, milk-based infant formula, applesauce and puree of peaches, pears, carrots, sweet potatoes, green beans, and squash were evaluated for total and speciated arsenic content. Arsenic concentrations found in rice-based cereals (63-320 ng/g dry weight) were similar to those reported for raw rice. Results for the analysis of powdered infant formula by inductively coupled plasma-mass spectrometry (ICP-MS) indicated a narrow and low arsenic concentration range (12 to 17 ng/g). Arsenic content in puree infant food products, including rice cereals, fruits, and vegetables, varies from <1 to 24 ng/g wet weight. Sample treatment with trifluoroacetic acid at 100 degrees C were an efficient and mild method for extraction of arsenic species present in different food matrixes as compared to alternative methods that included sonication and accelerated solvent extraction. Extraction recoveries from 94 to 128% were obtained when the summation of species was compared to total arsenic. The ion chromatography (IC)-ICP-MS method selected for arsenic speciation allowed for the quantitative determination of inorganic arsenic [As(III) + As(V)], dimethylarsinic acid (DMA), and methylarsonic acid (MMA). Inorganic arsenic and DMA are the main species found in rice-based and mixed rice/formula cereals, although traces of MMA were also detected. Inorganic arsenic was present in freeze-dried sweet potatoes, carrots, green beans, and peaches. MMA and DMA were not detected in these samples. Arsenic species in squash, pears, and applesauce were not detected above the method detection limit [5 ng/g dry weight for As(III), MMA, and DMA and 10 ng/g dry weight for As(V)].

Toward a theory of topopatric speciation: The role of genetic assortative mating

NASA Astrophysics Data System (ADS)

Schneider, David M.; do Carmo, Eduardo; Martins, Ayana B.; de Aguiar, Marcus A. M.

2014-09-01

We discuss a minimalist model of assortative mating for sexually reproducing haploid individuals with two biallelic loci. Assortativeness is introduced in the model by preventing mating between individuals whose alleles differ at both loci. Using methods of dynamical systems and population genetics we provide a full description of the evolution of the system for the case of very large populations. We derive the equations governing the evolution of haplotype frequencies and study the equilibrium solutions, stability, and speed of convergence to equilibrium. We find a constant of motion which allows us to introduce a geometrical construction that makes it straightforward to predict the fate of initial conditions. Finally, we discuss the consequences of this class of assortative mating models, including their possible extensions and implications for sympatric and topopatric speciation.

Recent Developments in the Speciation and Determination of Mercury Using Various Analytical Techniques

PubMed Central

Suvarapu, Lakshmi Narayana; Baek, Sung-Ok

2015-01-01

This paper reviews the speciation and determination of mercury by various analytical techniques such as atomic absorption spectrometry, voltammetry, inductively coupled plasma techniques, spectrophotometry, spectrofluorometry, high performance liquid chromatography, and gas chromatography. Approximately 126 research papers on the speciation and determination of mercury by various analytical techniques published in international journals since 2013 are reviewed. PMID:26236539

Rapid neo-sex chromosome evolution and incipient speciation in a major forest pest

Treesearch

Ryan R. Bracewell; Barbara J. Bentz; Brian T. Sullivan; Jeffrey M. Good

2017-01-01

Genome evolution is predicted to be rapid following the establishment of new (neo) sex chromosomes, but it is not known if neo-sex chromosome evolution plays an important role in speciation. Here we combine extensive crossing experiments with population and functional genomic data to examine neo-XY chromosome evolution and incipient speciation in the mountain pine...

Monte Carlo simulations of parapatric speciation

NASA Astrophysics Data System (ADS)

Schwämmle, V.; Sousa, A. O.; de Oliveira, S. M.

2006-06-01

Parapatric speciation is studied using an individual-based model with sexual reproduction. We combine the theory of mutation accumulation for biological ageing with an environmental selection pressure that varies according to the individuals geographical positions and phenotypic traits. Fluctuations and genetic diversity of large populations are crucial ingredients to model the features of evolutionary branching and are intrinsic properties of the model. Its implementation on a spatial lattice gives interesting insights into the population dynamics of speciation on a geographical landscape and the disruptive selection that leads to the divergence of phenotypes. Our results suggest that assortative mating is not an obligatory ingredient to obtain speciation in large populations at low gene flow.

Pleistocene phylogeographic effects on avian populations and the speciation process.

PubMed Central

Avise, J C; Walker, D

1998-01-01

Pleistocene biogeographic events have traditionally been ascribed a major role in promoting speciations and in sculpting the present-day diversity and distributions of vertebrate taxa. However, this paradigm has recently come under challenge from a review of interspecific mtDNA genetic distances in birds: most sister-species separations dated to the Pliocene. Here we summarize the literature on intraspecific mtDNA phylogeographic patterns in birds and reinterpret the molecular evidence bearing on Pleistocene influences. At least 37 of the 63 avian species surveyed (59%) are sundered into recognizable phylogeographic units, and 28 of these separations (76%) trace to the Pleistocene. Furthermore, use of phylogroup separation times within species as minimum estimates of 'speciation durations' also indicates that many protracted speciations, considered individually, probably extended through time from Pliocene origins to Pleistocene completions. When avian speciation is viewed properly as an extended temporal process rather than as a point event, Pleistocene conditions appear to have played an active role both in initiating major phylogeographic separations within species, and in completing speciations that had been inaugurated earlier. Whether the Pleistocene was exceptional in these regards compared with other geological times remains to be determined. PMID:9569664

Prevalence of disruptive selection predicts extent of species differentiation in Lake Victoria cichlids.

PubMed

van Rijssel, Jacco C; Moser, Florian N; Frei, David; Seehausen, Ole

2018-01-31

Theory suggests that speciation with gene flow is most likely when both sexual and ecological selection are divergent or disruptive. Divergent sexual and natural selection on the visual system have been demonstrated before in sympatric, morphologically similar sister species of Lake Victoria cichlids, but this does not explain the subtle morphological differences between them. To investigate the significance of natural selection on morphology during speciation, we here ask whether the prevalence of disruptive ecological selection differs between sympatric sister species that are at different stages of speciation. Some of our species pairs do ( Pundamilia ) and others do not ( Neochromis ) differ distinctively in sexually selected male nuptial coloration. We find that (i) evidence for disruptive selection, and for evolutionary response to it, is prevalent in traits that are differentiated between sister species; (ii) prevalence of both predicts the extent of genetic differentiation; and (iii) genetic differentiation is weaker in species pairs with conserved male nuptial coloration. Our results speak to the existence of two different mechanisms of speciation with gene flow: speciation mainly by sexual selection tightly followed by ecological character displacement in some cases and speciation mainly by divergent ecological selection in others. © 2018 The Author(s).

Comparative study of adaptive radiations with an example using parasitic flatworms (Platyhelminthes): Cercomeria

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brooks, D.R.; McLennan, D.A.

1993-11-01

Studies of adaptive radiations require robust phylogenies, estimates of species numbers for monophyletic groups within clades, assessments of the adaptive value of putative key innovations, and estimates of the frequency of speciation modes. Four criteria are necessary to identify an adaptive radiation within the parasitic platyhelminths: (1) a group contains significantly more species than its sister group, (2) species richness is apomorphic, (3) apomorphic traits enhance the potential for adaptively driven modes of speciation (sympatric speciation and speciation by peripheral isolation via host switching), and (4) the frequency of adaptively driven speciation modes is high within the group when comparedmore » with data from free-living groups. Only the species-rich Monogenea fulfill all four criteria. The Digenea and Eucestoda also are more species rich than their sister groups, their species richness is derived, and they possess unique characters that increase the potential for host switching to occur. However, because there is not enough information to determine whether the frequency of adaptive modes of speciation is high for those groups, we cannot yet assert that their radiations have been adaptive. 102 refs., 3 figs., 1 tab.« less

Speciation of strontium in particulates and sediments from the Mississippi River mixing zone

NASA Astrophysics Data System (ADS)

Xu, Yingfeng; Marcantonio, Franco

2004-06-01

Sequential extractions were performed on small amounts of particulate and sediment samples (6 to10 mg) from the Mississippi River mixing zone. The leachates were analyzed for Sr concentration and 87Sr/ 86Sr isotope ratio. Mn and Fe contents were also measured as their oxyhydroxides are potential carrier phases for Sr. The largest fraction of Sr in the solid phase (particulates and sediments) was found to be present in the residual, refractory fraction (>70% of total). By comparison with the corresponding sediment, particulates appear to have higher concentrations of nonresidual, labile Sr (30% vs. 15%). Carbonate components seem to play an important role as carriers for labile Sr in particulates and sediments. Changes in the composition and content of the solid phase may significantly modify both the 87Sr/ 86Sr isotope ratio of the total labile fractions and that of the bulk components. However, such modifications, under normal conditions, exert little measurable influence on the Sr isotope composition of the dissolved phase.

Mercury speciation and dispersion from an active gold mine at the West Wits area, South Africa.

PubMed

Lusilao-Makiese, J G; Tessier, E; Amouroux, D; Tutu, H; Chimuka, L; Weiersbye, I; Cukrowska, E M

2016-01-01

Total mercury (HgTOT), inorganic mercury (IHg), and methylmercury (MHg) were determined in dry season waters, sediments, and tailings from an active mine which has long history of gold exploitation. Although HgTOT in waters was generally low (0.03 to 19.60 ng L(-1)), the majority of the samples had proportions of MHg of at least 90 % of HgTOT which denotes a substantial methylation potential of the mine watersheds. Mercury was relatively high in tailing materials (up to 867 μg kg(-1)) and also in the mine sediments (up to 837 μg kg(-1)) especially in samples collected near tailing storage facilities and within a receiving water dam. Sediment profiles revealed mercury enrichment and enhanced methylation rate at deeper layers. The presence of IHg and decaying plants (organic matter) in the watersheds as well as the anoxic conditions of bulk sediments are believed to be some of the key factors favoring the mercury methylation at the site.

Non-invasive and micro-destructive investigation of the Domus Aurea wall painting decorations.

PubMed

Clementi, Catia; Ciocan, Valeria; Vagnini, Manuela; Doherty, Brenda; Tabasso, Marisa Laurenzi; Conti, Cinzia; Brunetti, Brunetto Giovanni; Miliani, Costanza

2011-10-01

The paper reports on the exploitation of an educated multi-technique analytical approach based on a wide non invasive step followed by a focused micro-destructive step, aimed at the minimally invasive identification of the pigments decorating the ceiling of the Gilded Vault of the Domus Aurea in Rome. The combination of elemental analysis with molecular characterization provided by X-ray fluorescence and UV-vis spectroscopies, respectively, allowed for the in situ non-invasive identification of a remarkable number of pigments, namely Egyptian blue, green earth, cinnabar, red ochre and an anthraquinonic lake. The study was completed with the Raman analysis of two bulk samples, in particular, SERS measurements allowed for the speciation of the anthraquinonic pigment. Elemental mapping by scanning electron microscopy-energy dispersive spectrometer combined with micro-fluorimetry on cross-section gave an insight into both the distribution of different blend of pigments and on the nature of the inorganic support of the red dye.

Inorganic speciation analysis of selenium by ion chromatography-inductively coupled plasma-mass spectrometry and its application to effluents from a petroleum refinery

NASA Astrophysics Data System (ADS)

Miekeley, Norbert; Pereira, Rogério C.; Casartelli, Evelton A.; Almeida, Ana C.; de F. B. Carvalho, Maria

2005-06-01

A new method for the speciation analysis of selenite (Se-IV), selenate (Se-VI), and selenocyanate (SeCN -) is described and first results are presented on the distribution of these species in wastewater samples from a Brazilian oil refinery plant. The method is based on the ion chromatographic separation of these species followed by on-line detection of 77Se, 78Se, and 82Se using quadrupole inductively coupled plasma-mass spectrometry (ICPMS). The system employed consisted of a HPLC pump equipped with a manual syringe loading injector, and an anion exchange column (Metrosep A Supp1), the latter interfaced with the ICPMS via a concentric nebulizer-cyclonic spray chamber sample introduction device. Several eluents already described in the literature for the speciation analysis of inorganic selenium were tested, permitting in most cases a good separation of Se(IV) and Se(VI), however, resulting all in very long residence times (> 30 min) and associated peak broadening for the SeCN - ion. This drawback could be effectively avoided by using as the mobile phase a solution of cyanuric acid (3 mmol L -1), modified with acetonitrile (2% v/v) and percchlorate acid (2.5 mmol L -1). Typical retention times (s) for the three analyte species were: selenite (210) < selenate (250) < selenocyanate (450). Repeatabilities in peak position were better than 1% and in peak area evaluation about 3%. Absolute limits of detection (in ng) for these species using an ELAN 5000 instrument and a 500-μL sample injection loop are 0.04, 0.05 and 0.09, respectively. No certified reference materials were available for this study, however, results on spiked wastewater samples showed acceptable recoveries (80-110%) and repeatabilities (RSD < 5%), thus validating this method for its intended purpose. Once optimized, the method was applied to wastewater samples from an oil refinery plant. In all samples until now analyzed, selenocyanate was by far the most abundant selenium species reaching concentrations of up to 90 μg L -1. Selenite was detected only in one sample and selenate could not identified in any of the samples analyzed. Total concentrations of selenium in most samples, assessed by hydride generation ICPMS and by solution nebulization inductively coupled plasma optical emission spectrometry (ICPOES), exceeded those obtained from speciation analysis, indicating the presence of other selenium species not observed by the here used methodology.

Carbon nanotubes grown on bulk materials and methods for fabrication

DOEpatents

Menchhofer, Paul A [Clinton, TN; Montgomery, Frederick C [Oak Ridge, TN; Baker, Frederick S [Oak Ridge, TN

2011-11-08

Disclosed are structures formed as bulk support media having carbon nanotubes formed therewith. The bulk support media may comprise fibers or particles and the fibers or particles may be formed from such materials as quartz, carbon, or activated carbon. Metal catalyst species are formed adjacent the surfaces of the bulk support material, and carbon nanotubes are grown adjacent the surfaces of the metal catalyst species. Methods employ metal salt solutions that may comprise iron salts such as iron chloride, aluminum salts such as aluminum chloride, or nickel salts such as nickel chloride. Carbon nanotubes may be separated from the carbon-based bulk support media and the metal catalyst species by using concentrated acids to oxidize the carbon-based bulk support media and the metal catalyst species.

Layered double hydroxides as the next generation inorganic anion exchangers: Synthetic methods versus applicability.

PubMed

Chubar, Natalia; Gilmour, Robert; Gerda, Vasyl; Mičušík, Matej; Omastova, Maria; Heister, Katja; Man, Pascal; Fraissard, Jacques; Zaitsev, Vladimir

2017-07-01

This work is the first report that critically reviews the properties of layered double hydroxides (LDHs) on the level of speciation in the context of water treatment application and dynamic adsorption conditions, as well as the first report to associate these properties with the synthetic methods used for LDH preparation. Increasingly stronger maximum allowable concentrations (MAC) of various contaminants in drinking water and liquid foodstuffs require regular upgrades of purification technologies, which might also be useful in the extraction of valuable substances for reuse in accordance with modern sustainability strategies. Adsorption is the main separation technology that allows the selective extraction of target substances from multicomponent solutions. Inorganic anion exchangers arrived in the water business relatively recently to achieve the newly approved standards for arsenic levels in drinking water. LDHs (or hydrotalcites, HTs) are theoretically the best anion exchangers due to their potential to host anions in their interlayer space, which increases their anion removal capacity considerably. This potential of the interlayer space to host additional amounts of target aqueous anions makes the LDHs superior to bulk anion exchanger. The other unique advantage of these layered materials is the flexibility of the chemical composition of the metal oxide-based layers and the interlayer anions. However, until now, this group of "classical" anion exchangers has not found its industrial application in adsorption and catalysis at the industrial scale. To accelerate application of LDHs in water treatment on the industrial scale, the authors critically reviewed recent scientific and technological knowledge on the properties and adsorptive removal of LDHs from water on the fundamental science level. This also includes review of the research tools useful to reveal the adsorption mechanism and the material properties beyond the nanoscale. Further, these properties are considered in association with the synthetic methods by which the LDHs were produced. Special attention is paid to the LDH properties that are particularly relevant to water treatment, such as exchangeability ease of the interlayer anions and the LDH stability at the solid-water interface. Notably, the LDH properties (e.g., rich speciation, hydration, and the exchangeability ease of the interlayer anions with aqueous anions) are considered in the synthetic strategy context applied to the material preparation. One such promising synthetic method has been developed by the authors who supported their opinions by the unpublished data in addition to reviewing the literature. The reviewing approach allowed for establishing regularities between the parameters: the LDH synthetic method-structure/surface/interlayer-removal-suitability for water treatment. Specifically, this approach allowed for a conclusion about either the unsuitability or promising potential of some synthetic methods (or the removal approaches) used for the preparation of LDHs for water purification at larger scales. The overall reviewing approach undertaken by the authors in this work mainly complements the other reviews on LDHs (published over the past seven to eight years) and for the first time compares the properties of these materials beyond the nanoscale. Copyright © 2017 Elsevier B.V. All rights reserved.

New method for the extraction of bulk channel mobility and flat-band voltage in junctionless transistors

NASA Astrophysics Data System (ADS)

Jeon, Dae-Young; Park, So Jeong; Mouis, Mireille; Barraud, Sylvain; Kim, Gyu-Tae; Ghibaudo, Gérard

2013-11-01

A new and simple method for the extraction of electrical parameters in junctionless transistors (JLTs) is presented. The bulk channel mobility (μbulk) and flat-band voltage (Vfb) were successfully extracted from the new method, based on a linear dependence between the inverse of transconductance squared (1/gm2) vs gate voltage in the partially depleted operation regime (Vth < Vg < Vfb). The validity of the new method is also proved by 2D numerical simulation and newly defined Maserjian's-like function for gm of JLT devices.

Geological and climatic forces driving speciation in the continentally distributed trilling chorus frogs (Pseudacris).

PubMed

Lemmon, Emily Moriarty; Lemmon, Alan R; Cannatella, David C

2007-09-01

Tertiary geological events and Quaternary climatic fluctuations have been proposed as important factors of speciation in the North American flora and fauna. Few studies, however, have rigorously tested hypotheses regarding the specific factors driving divergence of taxa. Here, we test explicit speciation hypotheses by correlating geologic events with divergence times among species in the continentally distributed trilling chorus frogs (Pseudacris). In particular, we ask whether marine inundation of the Mississippi Embayment, uplift of the Appalachian Mountains, or modification of the ancient Teays-Mahomet River system contributed to speciation. To examine the plausibility of ancient rivers causing divergence, we tested whether modern river systems inhibit gene flow. Additionally, we compared the effects of Quaternary climatic factors (glaciation and aridification) on levels of genetic variation. Divergence time estimates using penalized likelihood and coalescent approaches indicate that the major lineages of chorus frogs diversified during the Tertiary, and also exclude Quaternary climate change as a factor in speciation of chorus frogs. We show the first evidence that inundation of the Mississippi Embayment contributed to speciation. We reject the hypotheses that Cenozoic uplift of the Appalachians and that diversion of the Teays-Mahomet River contributed to speciation in this clade. We find that by reducing gene flow, rivers have the potential to cause divergence of lineages. Finally, we demonstrate that populations in areas affected by Quaternary glaciation and aridification have reduced levels of genetic variation compared to those from more equable regions, suggesting recent colonization.

A new cation-exchange method for accurate field speciation of hexavalent chromium

USGS Publications Warehouse

Ball, J.W.; McCleskey, R. Blaine

2003-01-01

A new method for field speciation of Cr(VI) has been developed to meet present stringent regulatory standards and to overcome the limitations of existing methods. The method consists of passing a water sample through strong acid cation-exchange resin at the field site, where Cr(III) is retained while Cr(VI) passes into the effluent and is preserved for later determination. The method is simple, rapid, portable, and accurate, and makes use of readily available, inexpensive materials. Cr(VI) concentrations are determined later in the laboratory using any elemental analysis instrument sufficiently sensitive to measure the Cr(VI) concentrations of interest. The new method allows measurement of Cr(VI) concentrations as low as 0.05 ??g 1-1, storage of samples for at least several weeks prior to analysis, and use of readily available analytical instrumentation. Cr(VI) can be separated from Cr(III) between pH 2 and 11 at Cr(III)/Cr(VI) concentration ratios as high as 1000. The new method has demonstrated excellent comparability with two commonly used methods, the Hach Company direct colorimetric method and USEPA method 218.6. The new method is superior to the Hach direct colorimetric method owing to its relative sensitivity and simplicity. The new method is superior to USEPA method 218.6 in the presence of Fe(II) concentrations up to 1 mg 1-1 and Fe(III) concentrations up to 10 mg 1-1. Time stability of preserved samples is a significant advantage over the 24-h time constraint specified for USEPA method 218.6.

Enhanced bulk heterojunction devices prepared by thermal and solvent vapor annealing processes

DOEpatents

Forrest, Stephen R.; Thompson, Mark E.; Wei, Guodan; Wang, Siyi

2017-09-19

A method of preparing a bulk heterojunction organic photovoltaic cell through combinations of thermal and solvent vapor annealing are described. Bulk heterojunction films may prepared by known methods such as spin coating, and then exposed to one or more vaporized solvents and thermally annealed in an effort to enhance the crystalline nature of the photoactive materials.

Bulk Enthalpy Calculations in the Arc Jet Facility at NASA ARC

NASA Technical Reports Server (NTRS)

Thompson, Corinna S.; Prabhu, Dinesh; Terrazas-Salinas, Imelda; Mach, Jeffrey J.

2011-01-01

The Arc Jet Facilities at NASA Ames Research Center generate test streams with enthalpies ranging from 5 MJ/kg to 25 MJ/kg. The present work describes a rigorous method, based on equilibrium thermodynamics, for calculating the bulk enthalpy of the flow produced in two of these facilities. The motivation for this work is to determine a dimensionally-correct formula for calculating the bulk enthalpy that is at least as accurate as the conventional formulas that are currently used. Unlike previous methods, the new method accounts for the amount of argon that is present in the flow. Comparisons are made with bulk enthalpies computed from an energy balance method. An analysis of primary facility operating parameters and their associated uncertainties is presented in order to further validate the enthalpy calculations reported herein.

Testing founder effect speciation: Divergence population genetics of the Spoonbills Platalea regia and Pl. minor (Threskiornithidae, Aves)

USGS Publications Warehouse

Yeung, Carol K.L.; Tsai, Pi-Wen; Chesser, R. Terry; Lin, Rong-Chien; Yao, Cheng-Te; Tian, Xiu-Hua; Li, Shou-Hsien

2011-01-01

Although founder effect speciation has been a popular theoretical model for the speciation of geographically isolated taxa, its empirical importance has remained difficult to evaluate due to the intractability of past demography, which in a founder effect speciation scenario would involve a speciational bottleneck in the emergent species and the complete cessation of gene flow following divergence. Using regression-weighted approximate Bayesian computation, we tested the validity of these two fundamental conditions of founder effect speciation in a pair of sister species with disjunct distributions: the royal spoonbill Platalea regia in Australasia and the black-faced spoonbill Pl. minor in eastern Asia. When compared with genetic polymorphism observed at 20 nuclear loci in the two species, simulations showed that the founder effect speciation model had an extremely low posterior probability (1.55 × 10-8) of producing the extant genetic pattern. In contrast, speciation models that allowed for postdivergence gene flow were much more probable (posterior probabilities were 0.37 and 0.50 for the bottleneck with gene flow and the gene flow models, respectively) and postdivergence gene flow persisted for a considerable period of time (more than 80% of the divergence history in both models) following initial divergence (median = 197,000 generations, 95% credible interval [CI]: 50,000-478,000, for the bottleneck with gene flow model; and 186,000 generations, 95% CI: 45,000-477,000, for the gene flow model). Furthermore, the estimated population size reduction in Pl. regia to 7,000 individuals (median, 95% CI: 487-12,000, according to the bottleneck with gene flow model) was unlikely to have been severe enough to be considered a bottleneck. Therefore, these results do not support founder effect speciation in Pl. regia but indicate instead that the divergence between Pl. regia and Pl. minor was probably driven by selection despite continuous gene flow. In this light, we discuss the potential importance of evolutionarily labile traits with significant fitness consequences, such as migratory behavior and habitat preference, in facilitating divergence of the spoonbills.

SPECIATION OF ARSENIC ANIMAL FEED ADDITIVES BY MICROBORE HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY WITH INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY

EPA Science Inventory

Phenylarsonic compounds have been used as poultry and swine feed additives for the purpose of growth promotion and disease prevention. Owing to the lack of suitable analytical methods, however, knowledge of their metabolism, environmental fate and impact remains incomplete. In or...

EMISSIONS INVENTORY OF PM 2.5 TRACE ELEMENTS ACROSS THE U.S.

EPA Science Inventory

This abstract describes work done to speciate PM_2.5 emissions into emissions of trace metals to enable concentrations of metal species to be predicted by air quality models. Methods are described and initial results are presented. A technique for validating the resul...

THE DEVELOPMENT AND APPLICATION OF AN IC-ICP-MS METHOD FOR THE SPECIATION OF METHYLTINS.

EPA Science Inventory

The determination of organotin compounds in environmental samples is of concern as the species have varying degrees of toxicity. Generally, the most toxic organotin compounds belong to the tri alkyl substituted variety followed by the di- and mono-substituted organotins. The low...

Speciation of cadmium and zinc with application to soil solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Holm, P.E.; Christensen, T.H.; Tjell, J.C.

1995-01-01

A two-part method has been developed for determination of Cd and Zn species in 50-mL soil solution samples containing low concentrations of Cd and Zn (1-10 {mu}g Cd L{sup -1} and 50-1000 {mu}g Zn L{sup -1}). The method uses two cation exchange resins (Amberlite CG 120 and Chelex 100) in a batch-column-batch procedure and relies on analytical determinations of Cd and Zn by graphite furnace atomic absorption spectrophotometry. The first part (batch) of the method allows determination of free divalent Cd{sup 2+} and Zn{sup 2+}. This part is experimentally sensitive to cation concentrations and ionic strength and these parameters shouldmore » be controlled during the experimental procedures. However, it is shown that Cd and Zn concentrations and pH do not influence the method. Speciations performed on samples containing chloride and sulfate were in accordance with theoretical calculations. The second part (column-batch) of the method operationally separates the complexed fraction into labile complexes, slowly labile complexes, and stable complexes. Chloro complexes were identified as labile complexes, while EDTA complexes were identified as stable complexes. The method works well with relatively small volumes of sample solutions and at low metal concentrations and may be useful in characterization of Cd and Zn in soil solutions. 12 refs., 6 figs., 3 tabs.« less

Pollinator shifts as triggers of speciation in painted petal irises (Lapeirousia: Iridaceae)

PubMed Central

Forest, Félix; Goldblatt, Peter; Manning, John C.; Baker, David; Colville, Jonathan F.; Devey, Dion S.; Jose, Sarah; Kaye, Maria; Buerki, Sven

2014-01-01

Background and Aims Adaptation to different pollinators has been hypothesized as one of the main factors promoting the formation of new species in the Cape region of South Africa. Other researchers favour alternative causes such as shifts in edaphic preferences. Using a phylogenetic framework and taking into consideration the biogeographical scenario explaining the distribution of the group as well as the distribution of pollinators, this study compares pollination strategies with substrate adaptations to develop hypotheses of the primary factors leading to speciation in Lapeirousia (Iridaceae), a genus of corm-bearing geophytes well represented in the Cape and presenting an important diversity of pollination syndromes and edaphic preferences. Methods Phylogenetic relationships are reconstructed within Lapeirousia using nuclear and plastid DNA sequence data. State-of-the-art methods in biogeography, divergence time estimation, character optimization and diversification rate assessments are used to examine the evolution of pollination syndromes and substrate shifts in the history of the group. Based on the phylogenetic results, ecological factors are compared for nine sister species pairs in Lapeirousia. Key Results Seventeen pollinator shifts and ten changes in substrate types were inferred during the evolution of the genus Lapeirousia. Of the nine species pairs examined, all show divergence in pollination syndromes, while only four pairs present different substrate types. Conclusions The available evidence points to a predominant influence of pollinator shifts over substrate types on the speciation process within Lapeirousia, contrary to previous studies that favoured a more important role for edaphic factors in these processes. This work also highlights the importance of biogeographical patterns in the study of pollination syndromes. PMID:24323246

Delimiting Species-Poor Data Sets using Single Molecular Markers: A Study of Barcode Gaps, Haplowebs and GMYC.

PubMed

Dellicour, Simon; Flot, Jean-François

2015-11-01

Most single-locus molecular approaches to species delimitation available to date have been designed and tested on data sets comprising at least tens of species, whereas the opposite case (species-poor data sets for which the hypothesis that all individuals are conspecific cannot by rejected beforehand) has rarely been the focus of such attempts. Here we compare the performance of barcode gap detection, haplowebs and generalized mixed Yule-coalescent (GMYC) models to delineate chimpanzees and bonobos using nuclear sequence markers, then apply these single-locus species delimitation methods to data sets of one, three, or six species simulated under a wide range of population sizes, speciation rates, mutation rates and sampling efforts. Our results show that barcode gap detection and GMYC models are unable to delineate species properly in data sets composed of one or two species, two situations in which haplowebs outperform them. For data sets composed of three or six species, bGMYC and haplowebs outperform the single-threshold and multiple-threshold versions of GMYC, whereas a clear barcode gap is only observed when population sizes and speciation rates are both small. The latter conditions represent a "sweet spot" for molecular taxonomy where all the single-locus approaches tested work well; however, the performance of these methods decreases strongly when population sizes and speciation rates are high, suggesting that multilocus approaches may be necessary to tackle such cases. © The Author(s) 2015. Published by Oxford University Press, on behalf of the Society of Systematic Biologists. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

A computational method for the coupled solution of reaction-diffusion equations on evolving domains and manifolds: Application to a model of cell migration and chemotaxis.

PubMed

MacDonald, G; Mackenzie, J A; Nolan, M; Insall, R H

2016-03-15

In this paper, we devise a moving mesh finite element method for the approximate solution of coupled bulk-surface reaction-diffusion equations on an evolving two dimensional domain. Fundamental to the success of the method is the robust generation of bulk and surface meshes. For this purpose, we use a novel moving mesh partial differential equation (MMPDE) approach. The developed method is applied to model problems with known analytical solutions; these experiments indicate second-order spatial and temporal accuracy. Coupled bulk-surface problems occur frequently in many areas; in particular, in the modelling of eukaryotic cell migration and chemotaxis. We apply the method to a model of the two-way interaction of a migrating cell in a chemotactic field, where the bulk region corresponds to the extracellular region and the surface to the cell membrane.

Great Salt Lake Composition and Rare Earth Speciation Analysis

DOE Data Explorer

Jiao, Yongqin; Lammers, Laura; Brewer, Aaron

2017-04-19

We have conducted aqueous speciation analyses of the Great Salt Lake (GSL) brine sample (Table 1) and a mock geo sample (Table 2) spiked with 1 ppb Tb and 100 ppb Tb. The GSL speciation (Figure 1) aligns with our basic speciation expectations that strong carbonate complexes would form at mid to higher pH's. Although we expected strong aqueous complexes with fluorides at neutral pH and with chlorides, and hydroxides at low pH, we observe that the dominant species in the low to mid pH range to be Tb3+ as a free ion. Still, we do see the presence of fluoride and chloride complexes within the expected low to mid pH range.

Advances in the Determination of the Speciation of the Carbon Associated with Biogenic Silica Produced by Plants

NASA Astrophysics Data System (ADS)

Masion, A.; Alexandre, A. E.; Ziarelli, F.; Viel, S.; Santos, G.

2016-12-01

Biogenic silica resulting from the precipitation of dissolved Si through biological processes in plants, often contains small amounts of occluded organic carbon. These phases, called phytoliths, have a long persistence in soils, making them tracers of past conditions. In this context, the knowledge of the carbon speciation associated with phytoliths bears significant importance in examining the carbon dynamics in soils. With carbon concentrations as low as the 0.1% range, examining the nature of organic carbon remains very challenging, and available tools (e.g. pyrolysis) are often prone to serious artifacts. Recent improvements of microwave sources enabled the application of the Dynamic Nuclear Polarization (DNP) technique to NMR, thereby establishing a new non-destructive tool for the qualitative and quantitative determination of the carbon speciation. Applied to the analysis of phytoliths, this method showed the presence of carbons from different sources within the sample: About 20% of the signal correspond to carbohydrates, and are assigned to photosynthetic carbon; the marked alkyl, N-alkyl and carbonyl signals indicate a significant proportion of proteins. This is consistent with the hypothesis that parts of the carbon associated with the phytoliths is imported into the host plant via uptake from the soil. Finally, lignins, glomalin-like and/or humic-like compounds are minor species associated with biogenic silica. This speciation was obtained overnight with a DNP-NMR set-up with an excellent sensitivity (few tens of weight ppm); the same spectrum on a standard NMR spectrometer would have required at least 250 days of data acquisition. The considerable gain in sensitivity associated with the use of DNP now makes NMR a relevant technique for the analysis of environmental samples.

Speciation Analysis of Arsenic by Selective Hydride Generation-Cryotrapping-Atomic Fluorescence Spectrometry with Flame-in-Gas-Shield Atomizer: Achieving Extremely Low Detection Limits with Inexpensive Instrumentation

PubMed Central

2015-01-01

This work describes the method of a selective hydride generation-cryotrapping (HG-CT) coupled to an extremely sensitive but simple in-house assembled and designed atomic fluorescence spectrometry (AFS) instrument for determination of toxicologically important As species. Here, an advanced flame-in-gas-shield atomizer (FIGS) was interfaced to HG-CT and its performance was compared to a standard miniature diffusion flame (MDF) atomizer. A significant improvement both in sensitivity and baseline noise was found that was reflected in improved (4 times) limits of detection (LODs). The yielded LODs with the FIGS atomizer were 0.44, 0.74, 0.15, 0.17 and 0.67 ng L–1 for arsenite, total inorganic, mono-, dimethylated As and trimethylarsine oxide, respectively. Moreover, the sensitivities with FIGS and MDF were equal for all As species, allowing for the possibility of single species standardization with arsenate standard for accurate quantification of all other As species. The accuracy of HG-CT-AFS with FIGS was verified by speciation analysis in two samples of bottled drinking water and certified reference materials, NRC CASS-5 (nearshore seawater) and SLRS-5 (river water) that contain traces of methylated As species. As speciation was in agreement with results previously reported and sums of all quantified species corresponded with the certified total As. The feasibility of HG-CT-AFS with FIGS was also demonstrated by the speciation analysis in microsamples of exfoliated bladder epithelial cells isolated from human urine. The results for the sums of trivalent and pentavalent As species corresponded well with the reference results obtained by HG-CT-ICPMS (inductively coupled plasma mass spectrometry). PMID:25300934

Responses of Mn2+ speciation in Deinococcus radiodurans and Escherichia coli to γ-radiation by advanced paramagnetic resonance methods

PubMed Central

Sharma, Ajay; Gaidamakova, Elena K.; Matrosova, Vera Y.; Bennett, Brian; Daly, Michael J.; Hoffman, Brian M.

2013-01-01

The remarkable ability of bacterium Deinococcus radiodurans to survive extreme doses of γ-rays (12,000 Gy), 20 times greater than Escherichia coli, is undiminished by loss of Mn-dependent superoxide dismutase (SodA). D. radiodurans radiation resistance is attributed to the accumulation of low-molecular-weight (LMW) “antioxidant” Mn2+–metabolite complexes that protect essential enzymes from oxidative damage. However, in vivo information about such complexes within D. radiodurans cells is lacking, and the idea that they can supplant reactive-oxygen-species (ROS)–scavenging enzymes remains controversial. In this report, measurements by advanced paramagnetic resonance techniques [electron-spin-echo (ESE)-EPR/electron nuclear double resonance/ESE envelope modulation (ESEEM)] reveal differential details of the in vivo Mn2+ speciation in D. radiodurans and E. coli cells and their responses to 10 kGy γ-irradiation. The Mn2+ of D. radiodurans exists predominantly as LMW complexes with nitrogenous metabolites and orthophosphate, with negligible EPR signal from Mn2+ of SodA. Thus, the extreme radiation resistance of D. radiodurans cells cannot be attributed to SodA. Correspondingly, 10 kGy irradiation causes no change in D. radiodurans Mn2+ speciation, despite the paucity of holo-SodA. In contrast, the EPR signal of E. coli is dominated by signals from low-symmetry enzyme sites such as that of SodA, with a minority pool of LMW Mn2+ complexes that show negligible coordination by nitrogenous metabolites. Nonetheless, irradiation of E. coli majorly changes LMW Mn2+ speciation, with extensive binding of nitrogenous ligands created by irradiation. We infer that E. coli is highly susceptible to radiation-induced ROS because it lacks an adequate supply of LMW Mn antioxidants. PMID:23536297

Mapping Asian anthropogenic emissions of non-methane volatile organic compounds to multiple chemical mechanisms

NASA Astrophysics Data System (ADS)

Li, M.; Zhang, Q.; Streets, D. G.; He, K. B.; Cheng, Y. F.; Emmons, L. K.; Huo, H.; Kang, S. C.; Lu, Z.; Shao, M.; Su, H.; Yu, X.; Zhang, Y.

2014-06-01

An accurate speciation mapping of non-methane volatile organic compounds (NMVOC) emissions has an important impact on the performance of chemical transport models (CTMs) in simulating ozone mixing ratios and secondary organic aerosols. Taking the INTEX-B Asian NMVOC emission inventory as the case, we developed an improved speciation framework to generate model-ready anthropogenic NMVOC emissions for various gas-phase chemical mechanisms commonly used in CTMs in this work, by using an explicit assignment approach and updated NMVOC profiles. NMVOC profiles were selected and aggregated from a wide range of new measurements and the SPECIATE database v.4.2. To reduce potential uncertainty from individual measurements, composite profiles were developed by grouping and averaging source profiles from the same category. The fractions of oxygenated volatile organic compounds (OVOC) were corrected during the compositing process for those profiles which used improper sampling and analyzing methods. Emissions of individual species were then lumped into species in different chemical mechanisms used in CTMs by applying mechanism-dependent species mapping tables, which overcomes the weakness of inaccurate mapping in previous studies. Emission estimates for individual NMVOC species differ between one and three orders of magnitude for some species when different sets of profiles are used, indicating that source profile is the most important source of uncertainties of individual species emissions. However, those differences are diminished in lumped species as a result of the lumping in the chemical mechanisms. Gridded emissions for eight chemical mechanisms at 30 min × 30 min resolution as well as the auxiliary data are available at http://mic.greenresource.cn/intex-b2006. The framework proposed in this work can be also used to develop speciated NMVOC emissions for other regions.

Phenotypic disparity in Iberian short-horned grasshoppers (Acrididae): the role of ecology and phylogeny.

PubMed

García-Navas, Vicente; Noguerales, Víctor; Cordero, Pedro J; Ortego, Joaquín

2017-05-04

The combination of model-based comparative techniques, disparity analyses and ecomorphological correlations constitutes a powerful method to gain insight into the evolutionary mechanisms that shape morphological variation and speciation processes. In this study, we used a time-calibrated phylogeny of 70 Iberian species of short-horned grasshoppers (Acrididae) to test for patterns of morphological disparity in relation to their ecology and phylogenetic history. Specifically, we examined the role of substrate type and level of ecological specialization in driving different aspects of morphological evolution (locomotory traits, chemosensitive organs and cranial morphology) in this recent radiation. We found a bimodal distribution of locomotory attributes corresponding to the two main substrate type guilds (plant vs. ground); plant-perching species tend to exhibit larger wings and thicker femora than those that remain on the ground. This suggests that life form (i.e., substrate type) is an important driving force in the evolution of morphological traits in short-horned grasshoppers, irrespective of ancestry. Substrate type and ecological specialization had no significant influence on head shape, a trait that showed a strong phylogenetic conservatism. Finally, we also found a marginal significant association between the length of antennae and the level of ecological specialization, suggesting that the development of sensory organs may be favored in specialist species. Our results provide evidence that even in taxonomic groups showing limited morphological and ecological disparity, natural selection seems to play a more important role than genetic drift in driving the speciation process. Overall, this study suggests that morphostatic radiations should not necessarily be considered as "non-adaptive" and that the speciation process can bind both adaptive divergence mechanisms and neutral speciation processes related with allopatric and/or reproductive isolation.

Speciation analysis of arsenic by selective hydride generation-cryotrapping-atomic fluorescence spectrometry with flame-in-gas-shield atomizer: achieving extremely low detection limits with inexpensive instrumentation.

PubMed

Musil, Stanislav; Matoušek, Tomáš; Currier, Jenna M; Stýblo, Miroslav; Dědina, Jiří

2014-10-21

This work describes the method of a selective hydride generation-cryotrapping (HG-CT) coupled to an extremely sensitive but simple in-house assembled and designed atomic fluorescence spectrometry (AFS) instrument for determination of toxicologically important As species. Here, an advanced flame-in-gas-shield atomizer (FIGS) was interfaced to HG-CT and its performance was compared to a standard miniature diffusion flame (MDF) atomizer. A significant improvement both in sensitivity and baseline noise was found that was reflected in improved (4 times) limits of detection (LODs). The yielded LODs with the FIGS atomizer were 0.44, 0.74, 0.15, 0.17 and 0.67 ng L(-1) for arsenite, total inorganic, mono-, dimethylated As and trimethylarsine oxide, respectively. Moreover, the sensitivities with FIGS and MDF were equal for all As species, allowing for the possibility of single species standardization with arsenate standard for accurate quantification of all other As species. The accuracy of HG-CT-AFS with FIGS was verified by speciation analysis in two samples of bottled drinking water and certified reference materials, NRC CASS-5 (nearshore seawater) and SLRS-5 (river water) that contain traces of methylated As species. As speciation was in agreement with results previously reported and sums of all quantified species corresponded with the certified total As. The feasibility of HG-CT-AFS with FIGS was also demonstrated by the speciation analysis in microsamples of exfoliated bladder epithelial cells isolated from human urine. The results for the sums of trivalent and pentavalent As species corresponded well with the reference results obtained by HG-CT-ICPMS (inductively coupled plasma mass spectrometry).

Metal-organic complexes in geochemical processes: temperature dependence of the standard thermodynamic properties of aqueous complexes between metal cations and dicarboxylate ligands

NASA Astrophysics Data System (ADS)

Prapaipong, Panjai; Shock, Everett L.; Koretsky, Carla M.

1999-10-01

By combining results from regression and correlation methods, standard state thermodynamic properties for aqueous complexes between metal cations and divalent organic acid ligands (oxalate, malonate, succinate, glutarate, and adipate) are evaluated and applied to geochemical processes. Regression of experimental standard-state equilibrium constants with the revised Helgeson-Kirkham-Flowers (HKF) equation of state yields standard partial molal entropies (S¯°) of aqueous metal-organic complexes, which allow determination of thermodynamic properties of the complexes at elevated temperatures. In cases where S¯° is not available from either regression or calorimetric measurement, the values of S¯° can be estimated from a linear correlation between standard partial molal entropies of association (ΔS¯°r) and standard partial molal entropies of aqueous cations (S¯°M). The correlation is independent of cation charge, which makes it possible to predict S¯° for complexes between divalent organic acids and numerous metal cations. Similarly, correlations between standard Gibbs free energies of association of metal-organic complexes (ΔḠ°r) and Gibbs free energies of formation (ΔḠ°f) for divalent metal cations allow estimates of standard-state equilibrium constants where experimental data are not available. These correlations are found to be a function of ligand structure and cation charge. Predicted equilibrium constants for dicarboxylate complexes of numerous cations were included with those for inorganic and other organic complexes to study the effects of dicarboxylate complexes on the speciation of metals and organic acids in oil-field brines. Relatively low concentrations of oxalic and malonic acids affect the speciation of cations more than similar concentrations of succinic, glutaric, and adipic acids. However, the extent to which metal-dicarboxylate complexes contribute to the speciation of dissolved metals depends on the type of dicarboxylic acid ligand; relative concentration of inorganic, mono-, and dicarboxylate ligands; and the type of metal cation. As an example, in the same solution, dicarboxylic acids have a greater influence on the speciation of Fe+2 and Mg+2 than on the speciation of Zn+2 and Mn+2.

Transformation of heavy metal speciation during sludge drying: mechanistic insights

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weng, Huanxin; Ma, Xue-Wen; Fu, Feng-Xia

2014-01-30

Speciation can fundamentally affect on the stability and toxicity of heavy metals in sludge from wastewater treatment plants. This research investigated the speciation of heavy metals in sludge from both municipal and industrial sources, and metal speciation change as a result of drying process to reduce sludge volume. The changes in sludge properties including sludge moisture content, temperature, density, and electrical conductivity were also monitored to provide insights into the mechanisms causing the change in heavy metal speciation. The results show that the drying process generally stabilized the Cr, Cu, Cd and Pb in sludge by transforming acid-soluble, reducible andmore » oxidizable species into structurally stable forms. Such transformation and stabilization occurred regardless of the sludge source and type, and were primarily caused by the changes in sludge properties associated with decomposition of organic matter and sulfide. The results enhanced our understanding of the geochemical behavior of heavy metals in municipal sludge, and are useful for designing a treatment system for environment-friendly disposal of sludge.« less

Parapatric speciation in three islands: dynamics of geographical configuration of allele sharing

PubMed Central

Iwasa, Yoh

2017-01-01

We studied the time to speciation by geographical isolation for a species living on three islands connected by rare migration. We assumed that incompatibility was controlled by a number of quantitative loci and that individuals differing in loci by more than a threshold did not mix genetically with each other. For each locus, we defined the geographical configuration (GC), which specifies islands with common alleles, and traced the stochastic transitions between different GCs. From these results, we calculated the changes in genetic distances. As a single migration event provides an opportunity for transitions in multiple loci, the GCs of different loci are correlated, which can be evaluated by constructing the stochastic differential equations of the number of loci with different GCs. Our model showed that the low number of incompatibility loci facilitates parapatric speciation and that migrants arriving as a group shorten the waiting time to speciation compared with the same number of migrants arriving individually. We also discuss how speciation rate changes with geographical structure. PMID:28386439

Multielemental speciation analysis by advanced hyphenated technique - HPLC/ICP-MS: A review.

PubMed

Marcinkowska, Monika; Barałkiewicz, Danuta

2016-12-01

Speciation analysis has become an invaluable tool in human health risk assessment, environmental monitoring or food quality control. Another step is to develop reliable multielemental speciation methodologies, to reduce costs, waste and time needed for the analysis. Separation and detection of species of several elements in a single analytical run can be accomplished by high performance liquid chromatography hyphenated to inductively coupled plasma mass spectrometry (HPLC/ICP-MS). Our review assembles articles concerning multielemental speciation determination of: As, Se, Cr, Sb, I, Br, Pb, Hg, V, Mo, Te, Tl, Cd and W in environmental, biological, food and clinical samples analyzed with HPLC/ICP-MS. It addresses the procedures in terms of following issues: sample collection and pretreatment, selection of optimal conditions for elements species separation by HPLC and determination using ICP-MS as well as metrological approach. The presented work is the first review article concerning multielemental speciation analysis by advanced hyphenated technique HPLC/ICP-MS. Copyright © 2016 Elsevier B.V. All rights reserved.

Biodegradation and speciation of residual SS-ethylenediaminedisuccinic acid (EDDS) in soil solution left after soil washing.

PubMed

Tandy, Susan; Ammann, Adrian; Schulin, Rainer; Nowack, Bernd

2006-07-01

This paper aims to investigate the degradation and speciation of EDDS-complexes (SS-ethylenediaminedisuccinic acid) in soil following soil washing. The changes in soil solution metal and EDDS concentrations were investigated for three polluted soils. EDDS was degraded after a lag phase of 7-11 days with a half-life of 4.18-5.60 days. No influence of EDDS-speciation on the reaction was observed. The decrease in EDDS resulted in a corresponding decrease in solubilized metals. Changes in EDDS speciation can be related to (1) initial composition of the soil, (2) temporarily anoxic conditions in the soil slurry after soil washing, (3) exchange of EDDS complexes with Cu even in soils without elevated Cu and (4) formation of NiEDDS. Dissolved organic matter is important for metal speciation at low EDDS concentrations. Our results show that even in polluted soils EDDS is degraded from a level of several hundred micromoles to below 1 microM within 50 days.

Genomic islands of divergence are not affected by geography of speciation in sunflowers.

PubMed

Renaut, S; Grassa, C J; Yeaman, S; Moyers, B T; Lai, Z; Kane, N C; Bowers, J E; Burke, J M; Rieseberg, L H

2013-01-01

Genomic studies of speciation often report the presence of highly differentiated genomic regions interspersed within a milieu of weakly diverged loci. The formation of these speciation islands is generally attributed to reduced inter-population gene flow near loci under divergent selection, but few studies have critically evaluated this hypothesis. Here, we report on transcriptome scans among four recently diverged pairs of sunflower (Helianthus) species that vary in the geographical context of speciation. We find that genetic divergence is lower in sympatric and parapatric comparisons, consistent with a role for gene flow in eroding neutral differences. However, genomic islands of divergence are numerous and small in all comparisons, and contrary to expectations, island number and size are not significantly affected by levels of interspecific gene flow. Rather, island formation is strongly associated with reduced recombination rates. Overall, our results indicate that the functional architecture of genomes plays a larger role in shaping genomic divergence than does the geography of speciation.

Synthesis of hexavalent molybdenum formo- and aceto-hydroxamates and deferoxamine via liquid-liquid metal partitioning

DOE Office of Scientific and Technical Information (OSTI.GOV)

Breshears, Andrew T.; Brown, M. Alex; Bloom, Ira

We report a new method of crystal growth and synthesis based on liquid-liquid partitioning that allows for isolation and in-depth characterization of molybdenyl bis(formohydroxamate), Mo-FHA, molybdenyl bis(acetohydroxamate), Mo-AHA, and molybdenyl deferoxamine, Mo-DFO, for the first time. This novel approach affords shorter crystal growth time (hourly timeframe) without sacrificing crystal size or integrity when other methods of crystallization were unsuccessful. All three Mo complexes are characterized in solution via FTIR, NMR, UV-vis, and EXAFS spectroscopy. Mo-AHA and Mo-FHA structures are resolved by single crystal X-ray diffraction. Using the molybdenyl hydroxamate structural information, the speciation of Mo in a siderophore complex (Mo-DFO)more » is determined via complimentary spectroscopic methods and confirmed by DFT calculations. ESI-MS verifies that a complex of 1:1 molybdenum to deferoxamine is present in solution. Additionally, the Mo solution speciation in the precursor organic phase, MoO2(NO3)2HEH[EHP]2 (where HEH[EHP] is 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester), is characterized by FTIR and EXAFS spectroscopy as well as DFT calculations.« less

Trace Element Speciation and Distribution Study at Shewanella oneidensis MR-1 Biofilm/Mineral/Water Interfaces

NASA Astrophysics Data System (ADS)

Gelabert, A.; Wang, Y.; Gescher, J.; Ha, J.; Cordova, C. D.; Singer, D. M.; Spormann, A. M.; Trainor, T. P.; Eng, P. J.; Brown, G. E.

2006-12-01

Fe- and Al-(oxyhydr)oxides are among the most reactive mineral surfaces contacted by surface and ground waters, and thus they constitute important sorbents for heavy metal and metalloid ions. As microbial biofilms may be present as coatings on these minerals, they are likely to induce major changes in surface charges and sorption capacities for metal(loid) ions compared to biofilm-free mineral surfaces. In addition, the micro- environments in biofilms can be quite different from those in bulk solutions, which can enhance (or inhibit) metal adsorption on mineral surfaces and produce biominerals that are not predicted by equilibrium thermodynamics based on the bulk solution values. In order to provide a more quantitative understanding of these effects, we have carried out a study of the interaction of Zn(II), Pb(II), and As(V) with Shewanella oneidensis (wild type, EPS-deficient mutant, and ppx- and ppk-deficient mutants) grown on highly polished and oriented single crystal surfaces of α-Al2O3 (1-102) and α-Fe2O3 (0001). This gram-negative bacterium commonly found in soil and sediments can use a wide range of electron donors and terminal electron acceptors including Fe(III) and Mn(IV) oxides under anaerobic conditions. In-situ ATR-FTIR analyses and potentiometric titrations of S. oneidensis biofilm collected from a glass bead-filled column inoculated with S. oneidensis were conducted in order to determine the nature of functional groups present on the bacterial surfaces, to quantify the site densities and protonation constants for these groups, and to determine the electrostatic parameters for S. oneidensis surfaces. GI-XAFS analyses performed on BL 11-2 at SSRL, together with macroscopic metal adsorption experiments as a function of pH (2 to 6.5), metal concentration (10-3 to 10-7 M), and ionic strength (10-1 to 10-3 M), were used to determine ion speciation and local coordination environments in the biofilm and to develop a surface complexation model describing the interactions among biofilm, metal(loid)s, and mineral surfaces. The long-period X-ray Standing Wave- fluorescent yield (XSW-FY) method, performed on BL ID-13-C at the APS, was used to obtain quantitative in situ information on the partitioning of Zn(II), Pb(II), and As(V) at these interfaces as a function of pH and ion concentration. XSW-FY results show that S. oneidensis biofilms do not block reactive sites on the hematite or alumina surfaces under our experimental conditions, which is consistent with the conclusion of our previous studies on trace element distributions at Burkholderia cepacia/mineral/water interfaces. Comparison of the observed trace element partitioning measured by XSW-FY with theoretical predictions of partitioning through thermodynamic models (using binding constants of metal(loid)s with the biofilm determined in this study and published binding constants of metal(loid)s with mineral substrates) allows us to describe biofilm local microenvironments and to understand how the biofilm coatings affect the reactivity of mineral surfaces.

Evidence for nonallopatric speciation among closely related sympatric Heliotropium species in the Atacama Desert

PubMed Central

Luebert, Federico; Jacobs, Pit; Hilger, Hartmut H; Muller, Ludo A H

2014-01-01

The genetic structure of populations of closely related, sympatric species may hold the signature of the geographical mode of the speciation process. In fully allopatric speciation, it is expected that genetic differentiation between species is homogeneously distributed across the genome. In nonallopatric speciation, the genomes may remain undifferentiated to a large extent. In this article, we analyzed the genetic structure of five sympatric species from the plant genus Heliotropium in the Atacama Desert. We used amplified fragment length polymorphisms (AFLPs) to characterize the genetic structure of these species and evaluate their genetic differentiation as well as the number of loci subject to positive selection using divergence outlier analysis (DOA). The five species form distinguishable groups in the genetic space, with zones of overlap, indicating that they are possibly not completely isolated. Among-species differentiation accounts for 35% of the total genetic differentiation (FST = 0.35), and FST between species pairs is positively correlated with phylogenetic distance. DOA suggests that few loci are subject to positive selection, which is in line with a scenario of nonallopatric speciation. These results support the idea that sympatric species of Heliotropium sect. Cochranea are under an ongoing speciation process, characterized by a fluctuation of population ranges in response to pulses of arid and humid periods during Quaternary times. PMID:24558582

Evidence for nonallopatric speciation among closely related sympatric Heliotropium species in the Atacama Desert.

PubMed

Luebert, Federico; Jacobs, Pit; Hilger, Hartmut H; Muller, Ludo A H

2014-02-01

The genetic structure of populations of closely related, sympatric species may hold the signature of the geographical mode of the speciation process. In fully allopatric speciation, it is expected that genetic differentiation between species is homogeneously distributed across the genome. In nonallopatric speciation, the genomes may remain undifferentiated to a large extent. In this article, we analyzed the genetic structure of five sympatric species from the plant genus Heliotropium in the Atacama Desert. We used amplified fragment length polymorphisms (AFLPs) to characterize the genetic structure of these species and evaluate their genetic differentiation as well as the number of loci subject to positive selection using divergence outlier analysis (DOA). The five species form distinguishable groups in the genetic space, with zones of overlap, indicating that they are possibly not completely isolated. Among-species differentiation accounts for 35% of the total genetic differentiation (F ST = 0.35), and F ST between species pairs is positively correlated with phylogenetic distance. DOA suggests that few loci are subject to positive selection, which is in line with a scenario of nonallopatric speciation. These results support the idea that sympatric species of Heliotropium sect. Cochranea are under an ongoing speciation process, characterized by a fluctuation of population ranges in response to pulses of arid and humid periods during Quaternary times.

Song evolution, speciation, and vocal learning in passerine birds.

PubMed

Mason, Nicholas A; Burns, Kevin J; Tobias, Joseph A; Claramunt, Santiago; Seddon, Nathalie; Derryberry, Elizabeth P

2017-03-01

Phenotypic divergence can promote reproductive isolation and speciation, suggesting a possible link between rates of phenotypic evolution and the tempo of speciation at multiple evolutionary scales. To date, most macroevolutionary studies of diversification have focused on morphological traits, whereas behavioral traits─including vocal signals─are rarely considered. Thus, although behavioral traits often mediate mate choice and gene flow, we have a limited understanding of how behavioral evolution contributes to diversification. Furthermore, the developmental mode by which behavioral traits are acquired may affect rates of behavioral evolution, although this hypothesis is seldom tested in a phylogenetic framework. Here, we examine evidence for rate shifts in vocal evolution and speciation across two major radiations of codistributed passerines: one oscine clade with learned songs (Thraupidae) and one suboscine clade with innate songs (Furnariidae). We find that evolutionary bursts in rates of speciation and song evolution are coincident in both thraupids and furnariids. Further, overall rates of vocal evolution are higher among taxa with learned rather than innate songs. Taken together, these findings suggest an association between macroevolutionary bursts in speciation and vocal evolution, and that the tempo of behavioral evolution can be influenced by variation in developmental modes among lineages. © 2016 The Author(s). Evolution © 2016 The Society for the Study of Evolution.

Tracking niche variation over millennial timescales in sympatric killer whale lineages

PubMed Central

Foote, Andrew D.; Newton, Jason; Ávila-Arcos, María C.; Kampmann, Marie-Louise; Samaniego, Jose A.; Post, Klaas; Rosing-Asvid, Aqqalu; Sinding, Mikkel-Holger S.; Gilbert, M. Thomas P.

2013-01-01

Niche variation owing to individual differences in ecology has been hypothesized to be an early stage of sympatric speciation. Yet to date, no study has tracked niche width over more than a few generations. In this study, we show the presence of isotopic niche variation over millennial timescales and investigate the evolutionary outcomes. Isotopic ratios were measured from tissue samples of sympatric killer whale Orcinus orca lineages from the North Sea, spanning over 10 000 years. Isotopic ratios spanned a range similar to the difference in isotopic values of two known prey items, herring Clupea harengus and harbour seal Phoca vitulina. Two proxies of the stage of speciation, lineage sorting of mitogenomes and genotypic clustering, were both weak to intermediate indicating that speciation has made little progress. Thus, our study confirms that even with the necessary ecological conditions, i.e. among-individual variation in ecology, it is difficult for sympatric speciation to progress in the face of gene flow. In contrast to some theoretical models, our empirical results suggest that sympatric speciation driven by among-individual differences in ecological niche is a slow process and may not reach completion. We argue that sympatric speciation is constrained in this system owing to the plastic nature of the behavioural traits under selection when hunting either mammals or fish. PMID:23945688

Tracking niche variation over millennial timescales in sympatric killer whale lineages.

PubMed

Foote, Andrew D; Newton, Jason; Ávila-Arcos, María C; Kampmann, Marie-Louise; Samaniego, Jose A; Post, Klaas; Rosing-Asvid, Aqqalu; Sinding, Mikkel-Holger S; Gilbert, M Thomas P

2013-10-07

Niche variation owing to individual differences in ecology has been hypothesized to be an early stage of sympatric speciation. Yet to date, no study has tracked niche width over more than a few generations. In this study, we show the presence of isotopic niche variation over millennial timescales and investigate the evolutionary outcomes. Isotopic ratios were measured from tissue samples of sympatric killer whale Orcinus orca lineages from the North Sea, spanning over 10 000 years. Isotopic ratios spanned a range similar to the difference in isotopic values of two known prey items, herring Clupea harengus and harbour seal Phoca vitulina. Two proxies of the stage of speciation, lineage sorting of mitogenomes and genotypic clustering, were both weak to intermediate indicating that speciation has made little progress. Thus, our study confirms that even with the necessary ecological conditions, i.e. among-individual variation in ecology, it is difficult for sympatric speciation to progress in the face of gene flow. In contrast to some theoretical models, our empirical results suggest that sympatric speciation driven by among-individual differences in ecological niche is a slow process and may not reach completion. We argue that sympatric speciation is constrained in this system owing to the plastic nature of the behavioural traits under selection when hunting either mammals or fish.

REE speciation in low-temperature acidic waters and the competitive effects of aluminum

USGS Publications Warehouse

Gimeno, Serrano M.J.; Auque, Sanz L.F.; Nordstrom, D. Kirk

2000-01-01

The effect of simultaneous competitive speciation of dissolved rare earth elements (REEs) in acidic waters (pH 3.3 to 5.2) has been evaluated by applying the PHREEQE code to the speciation of water analyses from Spain, Brazil, USA, and Canada. The main ions that might affect REE are Al3+, F-, SO42-, and PO43-. Fluoride, normally a significant complexer of REEs, is strongly associated with Al3+ in acid waters and consequently has little influence on REEs. The inclusion of aluminum concentrations in speciation calculations for acidic waters is essential for reliable speciation of REEs. Phosphate concentrations are too low (10-4 to 10-7 m) to affect REE speciation. Consequently, SO42- is the only important complexing ligand for REEs under these conditions. According to Millero [Millero, F.J., 1992. Stability constants for the formation of rare earth inorganic complexes as a function of ionic strength. Geochim. Cosmochim. Acta, 56, 3123-3132], the lanthanide sulfate stability constants are nearly constant with increasing atomic number so that no REE fractionation would be anticipated from aqueous complexation in acidic waters. Hence, REE enrichments or depletions must arise from mass transfer reactions. (C) 2000 Elsevier Science B.V. All rights reserved.

Primate diversification inferred from phylogenies and fossils.

PubMed

Herrera, James P

2017-12-01

Biodiversity arises from the balance between speciation and extinction. Fossils record the origins and disappearance of organisms, and the branching patterns of molecular phylogenies allow estimation of speciation and extinction rates, but the patterns of diversification are frequently incongruent between these two data sources. I tested two hypotheses about the diversification of primates based on ∼600 fossil species and 90% complete phylogenies of living species: (1) diversification rates increased through time; (2) a significant extinction event occurred in the Oligocene. Consistent with the first hypothesis, analyses of phylogenies supported increasing speciation rates and negligible extinction rates. In contrast, fossils showed that while speciation rates increased, speciation and extinction rates tended to be nearly equal, resulting in zero net diversification. Partially supporting the second hypothesis, the fossil data recorded a clear pattern of diversity decline in the Oligocene, although diversification rates were near zero. The phylogeny supported increased extinction ∼34 Ma, but also elevated extinction ∼10 Ma, coinciding with diversity declines in some fossil clades. The results demonstrated that estimates of speciation and extinction ignoring fossils are insufficient to infer diversification and information on extinct lineages should be incorporated into phylogenetic analyses. © 2017 The Author(s). Evolution © 2017 The Society for the Study of Evolution.

Hybridization masks speciation in the evolutionary history of the Galápagos marine iguana

PubMed Central

MacLeod, Amy; Rodríguez, Ariel; Vences, Miguel; Orozco-terWengel, Pablo; García, Carolina; Trillmich, Fritz; Gentile, Gabriele; Caccone, Adalgisa; Quezada, Galo; Steinfartz, Sebastian

2015-01-01

The effects of the direct interaction between hybridization and speciation—two major contrasting evolutionary processes—are poorly understood. We present here the evolutionary history of the Galápagos marine iguana (Amblyrhynchus cristatus) and reveal a case of incipient within-island speciation, which is paralleled by between-island hybridization. In-depth genome-wide analyses suggest that Amblyrhynchus diverged from its sister group, the Galápagos land iguanas, around 4.5 million years ago (Ma), but divergence among extant populations is exceedingly young (less than 50 000 years). Despite Amblyrhynchus appearing as a single long-branch species phylogenetically, we find strong population structure between islands, and one case of incipient speciation of sister lineages within the same island—ostensibly initiated by volcanic events. Hybridization between both lineages is exceedingly rare, yet frequent hybridization with migrants from nearby islands is evident. The contemporary snapshot provided by highly variable markers indicates that speciation events may have occurred throughout the evolutionary history of marine iguanas, though these events are not visible in the deeper phylogenetic trees. We hypothesize that the observed interplay of speciation and hybridization might be a mechanism by which local adaptations, generated by incipient speciation, can be absorbed into a common gene pool, thereby enhancing the evolutionary potential of the species as a whole. PMID:26041359

Bromine speciation in hydrous haplogranitic melts up to 7 GPa

NASA Astrophysics Data System (ADS)

Cochain, B.; de Grouchy, C.; Crepisson, C.; Kantor, I.; Irifune, T.; Sanloup, C.

2013-12-01

Halogens are minor volatiles in the Earth's mantle and crust, but they have significant and specific influences on magmatic and degassing processes. They also provide insights about subsurface magma movement and eruption likelihood in subduction-related volcanism. Their speciation in silicate melts affects volatile exsolution, rheology, and the thermodynamic properties of the melts but still remains relatively unknown. A few studies have explored halogen speciation at room conditions, i.e. in glasses but no firm conclusion has yet been reached. Furthermore, halogen speciation remains unexplored at high pressures and temperatures. In this work we investigate the speciation of Br in subduction-related melt (hydrous haplogranite melt) up to 1200°C and 7 GPa using X-ray absorption spectroscopy (XANES and EXAFS) at the Br K-edge. High P-T conditions were generated by the Paris-Edinburgh press. The use of nanocrystalline diamond capsules enabled us to avoid glitches in the EXAFS spectra. The results provide valuable information on Br speciation and its evolution with pressure. It gives insights into solubility mechanisms for halogens in magmas at depth and on their degassing from the melt. In addition, we were able to identify quench effects on the atomic environment of Br by comparison of high P-T in-situ spectra and ex-situ spectra recorded on quenched samples.

Speciation on a local geographic scale: the evolution of a rare rock outcrop specialist in Mimulus.

PubMed

Ferris, Kathleen G; Sexton, Jason P; Willis, John H

2014-08-05

Speciation can occur on both large and small geographical scales. In plants, local speciation, where small populations split off from a large-ranged progenitor species, is thought to be the dominant mode, yet there are still few examples to verify speciation has occurred in this manner. A recently described morphological species in the yellow monkey flowers, Mimulus filicifolius, is an excellent candidate for local speciation because of its highly restricted geographical range. Mimulus filicifolius was formerly identified as a population of M. laciniatus due to similar lobed leaf morphology and rocky outcrop habitat. To investigate whether M. filicifolius is genetically divergent and reproductively isolated from M. laciniatus, we examined patterns of genetic diversity in ten nuclear and eight microsatellite loci, and hybrid fertility in M. filicifolius and its purported close relatives: M. laciniatus, M. guttatus and M. nasutus. We found that M. filicifolius is genetically divergent from the other species and strongly reproductively isolated from M. laciniatus. We conclude that M. filicifolius is an independent rock outcrop specialist despite being morphologically and ecologically similar to M. laciniatus, and that its small geographical range nested within other wide-ranging members of the M. guttatus species complex is consistent with local speciation. © 2014 The Author(s) Published by the Royal Society. All rights reserved.

Characterization of Off-Road Diesel Emissions of Criteria Pollutants

DTIC Science & Technology

2008-10-01

Feasibility of soil dust source apportionment by the pyrolysis-gas chromatography/mass spectrometry method. J. Air Waste Manage. Assoc., 56(9):1230-1242...temperatures found in exhaust pipes. PM2.5 source profiles are important for speciated emission inventories and source apportionment , but few of these are...different between types. This method holds great potential for source apportionment , even in the absence of associating each pattern with a specific

Size exclusion chromatography with evaporative light scattering detection as a method for speciation analysis of polydimethylsiloxanes. III. Identification and determination of dimeticone and simeticone in pharmaceutical formulations.

PubMed

Mojsiewicz-Pieńkowska, Krystyna

2012-01-25

The pharmaceutical industry is one of the more important sectors for the use of polydimethylsiloxanes (PDMS), which belong to the organosilicon polymers. In drugs for internal use, they are used as an active pharmaceutical ingredient (API) called dimeticone or simeticone. Due to their specific chemical nature, PDMS can have different degrees of polymerization, which determine the molecular weight and viscosity. The Pharmacopoeial monographs for dimeticone and simeticone, only give the permitted polymerization and viscosity range. It is, however, essential to know also the degree of polymerization or the specific molecular weight of PDMS that are present in pharmaceutical formulations. In the literature there is information about the impact of particle size, and thus molecular weight, on the toxicity, absorption and migration in living organisms. This study focused on the use of a developed method - the exclusion chromatography with evaporative light scattering detector (SEC-ELSD) - for identification and determination of dimeticone and simeticone in various pharmaceutical formulations. The method had a high degree of specificity and was suitable for speciation analysis of these polymers. So far the developed method has not been used in the control of medicinal products containing dimeticone or simeticone. Copyright © 2011 Elsevier B.V. All rights reserved.

Speciation of the trivalent f-elements Eu(III) and Cm(III) in digestive media.

PubMed

Wilke, Claudia; Barkleit, Astrid; Stumpf, Thorsten; Ikeda-Ohno, Atsushi

2017-10-01

In case radioactive materials are released into the environment, their incorporation into our digestive system would be a significant concern. Trivalent f-elements, i.e., trivalent actinides and lanthanides, could potentially represent a serious health risk due to their chemo- and radiotoxicity, nevertheless the biochemical behavior of these elements are mostly unknown even to date. This study, therefore, focuses on the chemical speciation of trivalent f-elements in the human gastrointestinal tract. To simulate the digestive system artificial digestive juices (saliva, gastric juice, pancreatic juice and bile fluid) were prepared. The chemical speciation of lanthanides (as Eu(III)) and actinides (as Cm(III)) was determined experimentally by time-resolved laser-induced fluorescence spectroscopy (TRLFS) and the results were compared with thermodynamic modeling. The results indicate a dominant inorganic species with phosphate/carbonate in the mouth, while the aquo ion is predominantly formed with a minor contribution of the enzyme pepsin in the stomach. In the intestinal tract the most significant species are with the protein mucin. We demonstrated the first experimental results on the chemical speciation of trivalent f-elements in the digestive media by TRLFS. The results highlight a significant gap in chemical speciation between experiments and thermodynamic modeling due to the limited availability of thermodynamic stability constants particularly for organic species. Chemical speciation strongly influences the in vivo behavior of metal ions. Therefore, the results of this speciation study will help to enhance the assessment of health risks and to improve decorporation strategies after ingestion of these (radio-)toxic heavy metal ions. Copyright © 2017 Elsevier Inc. All rights reserved.

Chemical speciation using high energy resolution PIXE spectroscopy in the tender X-ray range

NASA Astrophysics Data System (ADS)

Kavčič, Matjaž; Petric, Marko; Vogel-Mikuš, Katarina

2018-02-01

High energy resolution X-ray emission spectroscopy employing wavelength dispersive (WDS) crystal spectrometers can provide energy resolution on the level of core-hole lifetime broadening of the characteristic emission lines. While crystal spectrometers have been traditionally used in combination with electron excitation for major and minor element analysis, they have been rarely considered in proton induced X-ray emission (PIXE) trace element analysis mainly due to low detection efficiency. Compared to the simplest flat crystal WDS spectrometer the efficiency can be improved by employing cylindrically or even spherically curved crystals in combination with position sensitive X-ray detectors. When such spectrometer is coupled to MeV proton excitation, chemical bonding effects are revealed in the high energy resolution spectra yielding opportunity to extend the analytical capabilities of PIXE technique also towards chemical state analysis. In this contribution we will focus on the high energy resolution PIXE (HR-PIXE) spectroscopy in the tender X-ray range performed in our laboratory with our home-built tender X-ray emission spectrometer. Some general properties of high energy resolution PIXE spectroscopy in the tender X-ray range are presented followed by an example of sulfur speciation in biological tissue illustrating the capabilities as well as limitations of HR-PIXE method used for chemical speciation in the tender X-ray range.

An expert system for chemical speciation of individual particles using low-Z particle electron probe X-ray microanalysis data.

PubMed

Ro, Chul-Un; Kim, HyeKyeong; Van Grieken, René

2004-03-01

An electron probe X-ray microanalysis (EPMA) technique, using an energy-dispersive X-ray detector with an ultrathin window, designated a low-Z particle EPMA, has been developed. The low-Z particle EPMA allows the quantitative determination of concentrations of low-Z elements, such as C, N, and O, as well as chemical elements that can be analyzed by conventional energy-dispersive EPMA, in individual particles. Since a data set is usually composed of data for several thousands of particles in order to make environmentally meaningful observations of real atmospheric aerosol samples, the development of a method that fully extracts chemical information contained in the low-Z particle EPMA data is important. An expert system that can rapidly and reliably perform chemical speciation from the low-Z particle EPMA data is presented. This expert system tries to mimic the logic used by experts and is implemented by applying macroprogramming available in MS Excel software. Its feasibility is confirmed by applying the expert system to data for various types of standard particles and a real atmospheric aerosol sample. By applying the expert system, the time necessary for chemical speciation becomes shortened very much and detailed information on particle data can be saved and extracted later if more information is needed for further analysis.

Inferring phylogeny and speciation of Gymnosporangium species, and their coevolution with host plants

PubMed Central

Zhao, Peng; Liu, Fang; Li, Ying-Ming; Cai, Lei

2016-01-01

Gymnosporangium species (Pucciniaceae, Pucciniales) cause serious diseases and significant economic losses to apple cultivars. Most of the reported species are heteroecious and complete their life cycles on two different plant hosts belonging to two unrelated genera, i.e. Juniperus and Malus. However, the phylogenetic relationships among Gymnosporangium species and the evolutionary history of Gymnosporangium on its aecial and telial hosts were still undetermined. In this study, we recognized species based on rDNA sequence data by using coalescent method of generalized mixed Yule-coalescent (GMYC) and Poisson Tree Processes (PTP) models. The evolutionary relationships of Gymnosporangium species and their hosts were investigated by comparing the cophylogenetic analyses of Gymnosporangium species with Malus species and Juniperus species, respectively. The concordant results of GMYC and PTP analyses recognized 14 species including 12 known species and two undescribed species. In addition, host alternations of 10 Gymnosporangium species were uncovered by linking the derived sequences between their aecial and telial stages. This study revealed the evolutionary process of Gymnosporangium species, and clarified that the aecial hosts played more important roles than telial hosts in the speciation of Gymnosporangium species. Host switch, losses, duplication and failure to divergence all contributed to the speciation of Gymnosporangium species. PMID:27385413

Selenium speciation in malt, wort, and beer made from selenium-biofortified two-rowed barley grain.

PubMed

Rodrigo, Sara; Santamaria, Oscar; Chen, Yi; McGrath, Steve P; Poblaciones, Maria J

2014-06-25

Selenium (Se) biofortification of barley is a suitable strategy to increase the Se concentration in grain. In the present paper, the suitability of this Se-biofortified grain for making Se-enriched beer is analyzed. The aim of the present study was to evaluate the effect of different Se fertilizer doses (0, 10, and 20 g of Se ha(-1)) and forms (sodium selenate or sodium selenite) on the Se loss during the malting and brewing processes and Se speciation in grain, malt, wort, and beer. Samples were analyzed using inductively coupled plasma-mass spectrometry (ICP-MS) and high-performance liquid chromatography (HPLC)-ICP-MS for total Se and speciation. Mashing-lautering was the process with the greatest Se loss (83.8%). After malting and brewing, only 7.3% of the initial Se was retained in beer, mainly in selenite form. Even so, the fertilizer application of sodium selenate at 20 g ha(-1) increased the total Se concentration almost 6-fold in the final beer in comparison to the use of grain derived from unfertilized barley. The present paper provides evidence that the use of Se-biofortified barley grain as a raw material to produce Se-enriched beer is possible, and the results are comparable to other methods in terms of efficiency.

Ligand exchange in ionic systems and its effect on silver nucleation and growth.

PubMed

Abbott, Andrew P; Azam, Muhammad; Frisch, Gero; Hartley, Jennifer; Ryder, Karl S; Saleem, Saima

2013-10-28

The electrodeposition of metals from ionic solutions is intrinsically linked to the reactivity of the solute ions. When metal salts dissolve, the exchange of the anion with the molecular and ionic components from solution affects the speciation and therefore the characteristics of metal reduction. This study investigates the nucleation mechanism, deposition kinetics, metal speciation and diffusion coefficients of silver salts dissolved in Deep Eutectic Solvents. The electrochemical reduction of AgCl, AgNO3 and Ag2O is studied in 1 : 2 choline chloride : ethylene glycol and 1 : 2 choline chloride : urea. Cyclic voltammetry is used to evaluate electrochemical kinetics. Detailed analysis of chronoamperometric data shows that silver deposits form via multiple 3D nucleation with mass transport controlled hemispherical growth. The nucleation mechanism was found to be potential dependent, varying from progressive to instantaneous as the reduction potential becomes more cathodic. Diffusion coefficients are determined using three different methods. Trends are rationalised in terms of solvent viscosity and silver speciation analysis with EXAFS. The morphology of electroreduced silver is investigated with scanning electron microscopy and shows that deposits from the urea based liquid form more dense morphologies than those from the ethylene glycol based liquid.

Energy saving control strategies for Haliscomenobacter hydrossis filamentous sludge bulking in the A/O process treating real low carbon/nitrogen domestic wastewater.

PubMed

Jiao, Erlong; Gao, Chundi; Li, Renfei; Tian, Ye; Peng, Yongzhen

2017-07-16

The control strategies of energy saving for filamentous sludge bulking were investigated in the A/O process under low dissolved oxygen (DO) with low carbon/nitrogen (C/N) ratio, and the dominant filamentous bacteria were identified by using fluorescent in situ hybridization. Initially, the sludge volume index reached nearly 500 mL/g and serious bulking occurred when the DO value was 0.5 mg/L, with Haliscomenobacter hydrossis as the major filamentous bacteria in the bulking sludge. Later on, the compartment number increased in the aerobic zone, increasing by this way DO, to control serious bulking. Increasing DO to 1 mg/L based on the increase of compartment number in the aerobic zone was the favorable controlling method, which solved the sludge loss, improved the effluent quality to the national discharge standard and allowed for energy costs saving. As a result, the effective control method for H. hydrossis filamentous sludge bulking provided the economical, convenient and longstanding method for most municipal wastewater treatment plants treating real low C/N domestic wastewater.

Iron speciation and redox state of mantle eclogites: Implications for ancient volatile cycles during mantle melting and oceanic crust subduction

NASA Astrophysics Data System (ADS)

Aulbach, Sonja; Woodand, Alan; Vasilyev, Prokopiy; Viljoen, Fanus

2017-04-01

Kimberlite-borne mantle eclogite xenoliths of Archaean and Palaeoproterozoic age are commonly interpreted as representing former oceanic crust. As such, they may retain a memory of the redox state of the ancient convecting mantle sources that gave rise to their magmatic protoliths and which controls the speciation of volatiles in planetary interiors. Mantle eclogite suites commonly include both cumulate and variably evolved extrusive varieties [1], which may be characterised by initial differences in Fe3+/Fetotal. Recent Fe-based oxybarometry shows mantle eclogites to have fO2 relative to the fayalite-magnetite-quartz buffer (ΔFMQ) of -3 to 0, whereby low fO2 relative to modern MORB may relate to subduction of more reducing Archaean oceanic crust or loss of ferric Fe during partial melt loss [2]. Indeed, using V/Sc as a redox proxy, it was recently shown that Archaean mantle eclogites are more reduced than modern MORB (ΔFMQ-1.3 vs. ΔFMQ -0.4) [3]. However, in the warmer ancient mantle, they were also subject to modification due to partial melt loss upon recycling and, after capture in the cratonic mantle lithosphere, may be overprinted by interaction with metasomatic melts and fluids. In order to help further constrain the redox state of mantle eclogites and unravel the effect of primary and secondary processes, we measured Fe3+/Fetotal by Mössbauer in garnet from mantle eclogites from the Lace kimberlite (Kaapvaal craton), comprising samples with melt- and cumulate-like oceanic crustal protoliths as well as metasomatised samples. Fe3+/ΣFe in garnet shows a strong negative correlation with jadeite content and bulk-rock Li and Cu abundances, suggesting increased partitioning of Fe3+ into jadeite in the presence of monovalent cations with which it can form coupled substitutions. Broad negative correlation with whole-rock Al2O3/TiO2 and positive correlation with ΣREE are interpreted as incompatible behaviour of Fe3+ during olivine-plagioclase accumulation (exclusion of TiO2 and REE). NMORB-normalised Nd/Yb, as a proxy of partial melt loss from subducting oceanic crust (<1) and metasomatism by typically LREE-enriched liquids (>1), shows no relationship with Fe3+/ΣFe. ΔFMQ, calculated using recently calibrated oxybarometers [2,4], broadly decreases with increasing pressure, which is ascribed to increasing garnet modes in metabasalts into which Fe3+ can be sequestered, similar to peridotite. The very low Fe3+/ΣFe, like V/Sc, appears to be a relatively robust indicator of low-pressure igneous processes and, potentially, the redox state of the ambient convecting mantle source to the protoliths of mantle eclogites. In contrast, Fe-based fO2 predominantly reflects pressure and bulk composition, and controls the speciation and mobility of volatiles in mafic heterogeneities during subduction and after emplacement in the cratonic mantle. The highly reduced nature of Archaean oceanic crust combined with further reduction upon pressure increase suggests that refractory graphite/diamond will be the stable carbon species. This may have prevented significant carbon output in Archaean subduction zones. [1] Aulbach and Jacob (2016) Lithos 262: 586-605; [2] Stagno et al. (2015) Contrib Mineral Petrol 42: 207-219; [3] Aulbach and Stagno (2016) Geology 44: 751-754; [4] Vasilyev (2016) PhD Thesis, Australian Nat Univ

Metal Ion Speciation and Dissolved Organic Matter Composition in Soil Solutions

NASA Astrophysics Data System (ADS)

Benedetti, M. F.; Ren, Z. L.; Bravin, M.; Tella, M.; Dai, J.

2014-12-01

Knowledge of the speciation of heavy metals and the role of dissolved organic matter (DOM) in soil solution is a key to understand metal mobility and ecotoxicity. In this study, soil column-Donnan membrane technique (SC-DMT) was used to measure metal speciation of Cd, Cu, Ni, Pb, and Zn in eighteen soil solutions, covering a wide range of metal sources and concentrations. DOM composition in these soil solutions was also determined. Our results show that in soil solution Pb and Cu are dominant in complex form, whereas Cd, Ni and Zn mainly exist as free ions; for the whole range of soil solutions, only 26.2% of DOM is reactive and consists mainly of fulvic acid (FA). The metal speciation measured by SC-DMT was compared to the predicted ones obtained via the NICA-Donnan model using the measured FA concentrations. The free ion concentrations predicted by speciation modelling were in good agreement with the measurements. Diffusive gradients in thin-films gels (DGT) were also performed to quantify the labile metal species in the fluxes from solid phase to solution in fourteen soils. The concentrations of metal species detected by DGT were compared with the free ion concentrations measured by DMT and the maximum concentrations calculated based on the predicted metal speciation in SC-DMT soil solutions. It is concluded that both inorganic species and a fraction of FA bound species account for the amount of labile metals measured by DGT, consistent with the dynamic features of this technique. The comparisons between measurements using analytical techniques and mechanistic model predictions provided mutual validation in their performance. Moreover, we show that to make accurate modelling of metal speciation in soil solutions, the knowledge of DOM composition is the crucial information, especially for Cu; like in previous studies the modelling of Pb speciation is not optimal and an updated of Pb generic binding parameters is required to reduce model prediction uncertainties.

Sewage treatment method and apparatus

DOE Office of Scientific and Technical Information (OSTI.GOV)

Engelmann, J.A.

1982-07-13

A method and apparatus for treating sewage and converting the sewage into organic fertilizer which utilizes equipment for converting the solid material of the sewage into patties and a mixing apparatus for mixing the patties with bulking agents. The mixture of patties and bulking agents is stored in a pile and subjected to a supply of air to enhance the self-combustion or oxidation of the organic material in the patties. The bulking agents provide the patty-bulking agent mixture with air passages and pockets and minimize compaction of the patties. The selfcombustion of the patties continues until the organic material ismore » burned out, leaving a residual ash. A shaker separator having an elongated longitudinal perforated member is reciprocated to separate the ash from the bulking agents. The ash is collected and utilized as organic fertilizer. The bulking agents are recycled back to the mixing apparatus.« less

Formation and Stability of Bulk Nanobubbles Generated by Ethanol-Water Exchange.

PubMed

Qiu, Jie; Zou, Zhenglei; Wang, Shuo; Wang, Xingya; Wang, Lei; Dong, Yaming; Zhao, Hongwei; Zhang, Lijuan; Hu, Jun

2017-05-19

Bulk nanobubbles have unique properties and find potential applications in many important processes. However, their stability or long lifetime still needs to be understood and has attracted much attention from researchers. Bulk nanobubbles are generated based on ethanol-water exchange, a method that is generally used in the study of surface nanobubbles. Their formation and stability is further studied by using a new type of dynamic light scattering known as NanoSight. The results show that the concentration of the bulk nanobubbles produced by this method is about five times greater than that in the degassed group, which indicates the existence of bulk gas nanobubbles. The effects of ethanol/water ratios and temperature on the stability of the bulk nanobubbles have also been studied and their numbers reach a maximum at a ratio of about 1:10 (v/v). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Estimating carbon and nitrogen pools in a forest soil: Influence of soil bulk density methods and rock content

Treesearch

Martin F. Jurgensen; Deborah S. Page-Dumroese; Robert E. Brown; Joanne M. Tirocke; Chris A. Miller; James B. Pickens; Min Wang

2017-01-01

Soils with high rock content are common in many US forests, and contain large amounts of stored C. Accurate measurements of soil bulk density and rock content are critical for calculating and assessing changes in both C and nutrient pool size, but bulk density sampling methods have limitations and sources of variability. Therefore, we evaluated the use of small-...

Use of Mössbauer spectroscopy to determine the effect of salinity on the speciation of triorganotins in Anacostia River sediments

NASA Astrophysics Data System (ADS)

Eng, George; Song, Xueqing; May, Leopold

2006-06-01

The speciation of several tributyltin and triphenyltin compounds under varying salinity conditions (0, 20, 40 and 60%) was studied by Mössbauer spectroscopy in both anaerobic and aerobic Anacostia River sediments. The Mössbauer spectral parameters of the spiked sediments indicated that changes in the salinity did not affect the speciation of the tin compounds in either aerobic or anaerobic sediments.

Use of Mössbauer spectroscopy to determine the effect of salinity on the speciation of triorganotins in Anacostia River sediments

NASA Astrophysics Data System (ADS)

Eng, George; Song, Xueqing; May, Leopold

The speciation of several tributyltin and triphenyltin compounds under varying salinity conditions (0, 20, 40 and 60%) was studied by Mössbauer spectroscopy in both anaerobic and aerobic Anacostia River sediments. The Mössbauer spectral parameters of the spiked sediments indicated that changes in the salinity did not affect the speciation of the tin compounds in either aerobic or anaerobic sediments.

Biology and toxicology of tellurium explored by speciation analysis.

PubMed

Ogra, Yasumitsu

2017-05-24

Tellurium (Te) is widely used in industry because it has unique physicochemical properties. Although Te is a non-essential element in animals and plants, it is expected to be metabolized to organometallic compounds having a carbon-Te bond in living organisms exposed to inorganic Te compounds. Thus, the speciation and identification of tellurometabolites are expected to contribute to the depiction of the metabolic chart of Te. Speciation by elemental mass spectrometry and identification by molecular mass spectrometry coupled with separation techniques have significantly contributed to the discovery of tellurometabolites in animals and plants. The aim of this mini review is to present recent advances in the biology and toxicology of tellurium as revealed by speciation and identification by molecular mass spectrometry.

Composition of COH fluids at 1 GPa: an experimental study on speciation and solubility

NASA Astrophysics Data System (ADS)

Tiraboschi, Carla; Tumiati, Simone; Recchia, Sandro; Ulmer, Peter; Pettke, Thomas; Fumagalli, Patrizia; Poli, Stefano

2014-05-01

COH fluids play a fundamental role in many geological processes, controlling the location of melting in subduction zones and promoting mass transfer from the subducting litosphere to the overlying mantle wedge. The properties of COH fluids are strictly dependent on the composition of the fluid in subduction systems, i.e., the speciation of the volatile components of the fluid itself and the presence of solutes deriving from the dissolution of rock-forming minerals. In the scientific literature, the speciation of COH fluids has been generally determined through thermodynamic calculations using equations of state of simple H2O-non-polar gas systems (e.g., H2O-CO2-CH4), equations that do not consider the complexity related to dissolution processes, which are substantially unexplored in COH fluids and limited so far to aqueous fluids (Newton & Manning, 2002). The aim of this work is to investigate experimentally the speciation and the dissolution of mantle minerals in carbon-saturated COH fluids at buffered fO2 conditions. Our experimental approach relies on two different techniques: 1) analysis by means of quadrupole mass spectrometer (QMS) of the fluids from pierced run capsules to retrieve speciation of volatile components and 2) analysis of frozen COH fluid with laser-ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) to measure the amount of solutes. Experiments were conducted at pressure of 1 GPa and temperatures from 800 to 900° C using a rocking piston cylinder apparatus. Mantle minerals in equilibrium with COH fluid are represented by synthetic forsterite. fO2 conditions were controlled using the double capsule technique and NNO buffer (ΔFMQ=-0.61 at 800° C; ΔFMQ =-0.98 at 900° C). For the speciation experiments, oxalic acid dihydrate and graphite have been used to generate carbon-saturated COH fluid. The speciation was determined by analyzing the quenched COH fluid, retrieved by piercing the capsule in a gas-tight vessel at T =80° C and convoying evolved gases to a QMS through a heated line to avoid the condensation of water. This type of analyzer ensures superior performances in terms of selectivity of molecules to be detected, high acquisition rates and extended linear response range. The influence of dissolved solutes on fluid speciation has been evaluated by comparing experiments in the pure COH system and in the COH+forsterite system. To determine the solubility of forsterite in COH fluids we performed a second set of experiments at the same P , T and fO2 conditions above. Fluids trapped in a diamond layer were analysed by the cryogenic LA-ICP-MS technique described by Aerts et al. (2010). With this method the aqueous part of the COH fluid is frozen prior the opening and maintained frozen during the analysis to avoid any precipitation of solutes. The results will highlight the importance of fluids for the mass transport in subduction zones. Comparison between experimental data and thermodynamic calculation will also be shown. References: Aerts, M., Hack, A.C., Reusser, E., Ulmer, P. (2010) Am. Mineral. 95, 1523-1526. Newton, R.C., Manning, C.E. (2002) Geochim. Cosmochim. Ac. 66, 4165-4176.

FY06 ORD PILOT STUDY: DETERMINE BIOAVAILABILITY AND BIOACCESSIBILITY OF ARSENIC IN SOIL AND DEVELOP ARSENIC SPECIATION METHODS

EPA Science Inventory

The product is a presentation requested by the organizers of the 2005 US EPA Bioavailability Technical Review Workgroup. It presents an overview, approaches (in-vivo & in-vitro), and logistics of the ORD pilot study on bioavailability of arsenic in soil. The overall project was ...

Measurement of air-surface exchange of speciated nitrogen and sulfur compounds using a modified MARGA 2S: Assessment and control of data quality

EPA Science Inventory

Improved measurement methods are needed to characterize dry deposition of sulfur and nitrogen compounds to assess ecosystem exposure to nutrients and acidifying compounds and to develop atmospheric deposition budgets in support of critical loads assessments. The purpose of this ...

Inorganic selenium speciation analysis in Allium and Brassica vegetables by ionic liquid assisted liquid-liquid microextraction with multivariate optimization.

PubMed

Castro Grijalba, Alexander; Martinis, Estefanía M; Wuilloud, Rodolfo G

2017-03-15

A highly sensitive vortex assisted liquid-liquid microextraction (VA-LLME) method was developed for inorganic Se [Se(IV) and Se(VI)] speciation analysis in Allium and Brassica vegetables. Trihexyl(tetradecyl)phosphonium decanoate phosphonium ionic liquid (IL) was applied for the extraction of Se(IV)-ammonium pyrrolidine dithiocarbamate (APDC) complex followed by Se determination with electrothermal atomic absorption spectrometry. A complete optimization of the graphite furnace temperature program was developed for accurate determination of Se in the IL-enriched extracts and multivariate statistical optimization was performed to define the conditions for the highest extraction efficiency. Significant factors of IL-VA-LLME method were sample volume, extraction pH, extraction time and APDC concentration. High extraction efficiency (90%), a 100-fold preconcentration factor and a detection limit of 5.0ng/L were achieved. The high sensitivity obtained with preconcentration and the non-chromatographic separation of inorganic Se species in complex matrix samples such as garlic, onion, leek, broccoli and cauliflower, are the main advantages of IL-VA-LLME. Copyright © 2016 Elsevier Ltd. All rights reserved.

Mercury speciation by differential photochemical vapor generation at UV-B vs. UV-C wavelength

NASA Astrophysics Data System (ADS)

Chen, Guoying; Lai, Bunhong; Mei, Ni; Liu, Jixin; Mao, Xuefei

2017-11-01

Photochemical vapor generation (PVG) is an effective sample introduction scheme for volatile mercury (Hg). Speciation of Hg++ and MeHg+ was fulfilled for the first time by differential PVG under UV-B vs. UV-C wavelength and applied to fish oil supplements. After liquid-liquid extraction, the aqueous extract was mixed with 0.4% anthranilic acid (AA)-20% formic acid (FA) in a quartz coil, and exposed sequentially to 311 nm or 254 nm UV light. The resulting Hg0 vapor was detected by atomic fluorescence spectrometry (AFS). At each wavelength, the AFS intensity was a linear function of Hg++ and MeHg+ concentrations, which were solvable from a set of two equations. This method achieved ultrahigh sensitivity with 0.50 and 0.63 ng mL- 1 limits of detection for Hg++ and MeHg+, respectively, and 73% recovery for MeHg+ at 10 ng mL- 1. Validation was performed by ICP-MS on total Hg. Obviation of chemical or chromatographic separation rendered this method rapid, green, and cost-effective.

Coupled high performance liquid chromatography-microwave digestion-hydride generation-atomic absorption spectrometry for inorganic and organic arsenic speciation in fish tissue.

PubMed

Villa-Lojo, M C; Alonso-Rodríguez, E; López-Mahía, P; Muniategui-Lorenzo, S; Prada-Rodríguez, D

2002-06-10

A high performance liquid chromatography-microwave digestion-hydride generation-atomic absorption spectrometry (HPLC-MW-HG-AAS) coupled method is described for As(III), As(V), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), arsenobetaine (AsB) and arsenocholine (AsC) determination. A Hamilton PRP-X100 anion-exchange column is used for carrying out the arsenic species separation. As mobile phase 17 mM phosphate buffer (pH 6.0) is used for As(III), As(V), MMA and DMA separation, and ultrapure water (pH 6.0) for AsB and AsC separation. Prior to injection into the HPLC system AsB and AsC are isolated from the other arsenic species using a Waters Accell Plus QMA cartridge. A microwave digestion with K(2)S(2)O(8) as oxidizing agent is used for enhancing the efficiency of conversion of AsB and AsC into arsenate. Detection limits achieved were between 0.3 and 1.1 ng for all species. The method was applied to arsenic speciation in fish samples.

Equilibrium Speciation of Select Lanthanides in the Presence of Acidic Ligands in Homo- and Heterogeneous Solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Robinson, Troy A

2011-08-01

This dissertation explores lanthanide speciation in liquid solution systems related to separation schemes involving the acidic ligands: bis(2-ethylhexyl) phosphoric acid (HDEHP), lactate, and 8-hydroxyquinoline. Equilibrium speciation of neodymium (Nd 3+), sodium (Na+), HDEHP, water, and lactate in the TALSPEAK liquid-liquid extraction system was explored under varied Nd 3+ loading of HDEHP in the organic phase and through extraction from aqueous HCl and lactate media. System speciation was probed through vapor pressure osmometry, visible and Fourier Transform Infrared (FTIR) spectroscopy, 22Na and 13C labeled lactate radiotracer distribution measurements, Karl Fischer titrations, and equilibrium pH measurements. Distribution of Nd 3+, Na +,more » lactate, and equilibrium pH were modeled using the SXLSQI software to obtain logKNd and logKNa extraction constants under selected conditions. Results showed that high Nd 3+ loading of the HDEHP led to Nd 3+ speciation that departs from the ion exchange mechanism and includes formation of highly aggregated, polynuclear [NdLactate(DEHP) 2] x; (with x > 1). By substituting lanthanum (La 3+) for Nd 3+ in this system, NMR scoping experiments using 23Na, 31P nuclei and 13C labeled lactate were performed. Results indicated that this technique is sensitive to changes in system speciation, and that further experiments are warranted. In a homogeneous system representing the TALSPEAK aqueous phase, Lactate protonation behavior at various temperatures was characterized using a combination of potentiometric titration and modeling with the Hyperquad computer program. The temperature dependent deprotonation behavior of lactate showed little change with temperature at 2.0 M NaCl ionic strength. Cloud point extraction is a non-traditional separation technique that starts with a homogeneous phase that becomes heterogeneous by the micellization of surfactants through the increase of temperature. To better understand the behavior of europium (Eu 3+) and 8-hydroxyquinoline under cloud point extraction conditions, potentiometric and spectrophotometric titrations coupled with modeling with Hyperquad and SQUAD computer programs were performed to assess europium (Eu 3+) and 8-hydroxyquinoline speciation. Experiments in both water and a 1wt% Triton X-114/water mixed solvent were compared to understand the effect of Triton X-114 on the system speciation. Results indicated that increased solvation of 8-hydroxyquinoline by the mixed solvent lead to more stable complexes involving 8-hydroxyquinoline than in water, whereas competition between hydroxide and Triton X-114 for Eu 3+ led to lower stability hydrolysis complexes in the mixed solvent than in water. Lanthanide speciation is challenging due to the trivalent oxidation state that leads to multiple ligand complexes, including some mixed complexes. The complexity of the system demands well-designed and precise experiments that capture the nuances of the chemistry. This work increased the understanding of lanthanide speciation in the explored systems, but more work is required to produce a comprehensive understanding of the speciation involved.« less

The existence of species rests on a metastable equilibrium between inbreeding and outbreeding. An essay on the close relationship between speciation, inbreeding and recessive mutations

PubMed Central

2011-01-01

Background Speciation corresponds to the progressive establishment of reproductive barriers between groups of individuals derived from an ancestral stock. Since Darwin did not believe that reproductive barriers could be selected for, he proposed that most events of speciation would occur through a process of separation and divergence, and this point of view is still shared by most evolutionary biologists today. Results I do, however, contend that, if so much speciation occurs, the most likely explanation is that there must be conditions where reproductive barriers can be directly selected for. In other words, situations where it is advantageous for individuals to reproduce preferentially within a small group and reduce their breeding with the rest of the ancestral population. This leads me to propose a model whereby new species arise not by populations splitting into separate branches, but by small inbreeding groups "budding" from an ancestral stock. This would be driven by several advantages of inbreeding, and mainly by advantageous recessive phenotypes, which could only be retained in the context of inbreeding. Reproductive barriers would thus not arise as secondary consequences of divergent evolution in populations isolated from one another, but under the direct selective pressure of ancestral stocks. Many documented cases of speciation in natural populations appear to fit the model proposed, with more speciation occurring in populations with high inbreeding coefficients, and many recessive characters identified as central to the phenomenon of speciation, with these recessive mutations expected to be surrounded by patterns of limited genomic diversity. Conclusions Whilst adaptive evolution would correspond to gains of function that would, most of the time, be dominant, this type of speciation by budding would thus be driven by mutations resulting in the advantageous loss of certain functions since recessive mutations very often correspond to the inactivation of a gene. A very important further advantage of inbreeding is that it reduces the accumulation of recessive mutations in genomes. A consequence of the model proposed is that the existence of species would correspond to a metastable equilibrium between inbreeding and outbreeding, with excessive inbreeding promoting speciation, and excessive outbreeding resulting in irreversible accumulation of recessive mutations that could ultimately only lead to extinction. Reviewer names Eugene V. Koonin, Patrick Nosil (nominated by Dr Jerzy Jurka), Pierre Pontarotti PMID:22152499

Allochronic speciation, secondary contact, and reproductive character displacement in periodical cicadas (Hemiptera: Magicicada spp.): genetic, morphological, and behavioural evidence.

PubMed

Cooley, J R; Simon, C; Marshall, D C; Slon, K; Ehrhardt, C

2001-03-01

Periodical cicadas have proven useful in testing a variety of ecological and evolutionary hypotheses because of their unusual life history, extraordinary abundance, and wide geographical range. Periodical cicadas provide the best examples of synchronous periodicity and predator satiation in the animal kingdom, and are excellent illustrations of habitat partitioning (by the three morphologically distinct species groups), incipient species (the year classes or broods), and cryptic species (a newly discovered 13-year species, Magicicada neotredecim). They are particularly useful for exploring questions regarding speciation via temporal isolation, or allochronic speciation. Recently, data were presented that provided strong support for an instance of allochronic speciation by life-cycle switching. This speciation event resulted in the formation of a new 13-year species from a 17-year species and led to secondary contact between two formerly separated lineages, one represented by the new 13-year cicadas (and their 17-year ancestors), and the other represented by the pre-existing 13-year cicadas. Allozyme frequency data, mitochondrial DNA (mtDNA), and abdominal colour were shown to be correlated genetic markers supporting the life-cycle switching/allochronic speciation hypothesis. In addition, a striking pattern of reproductive character displacement in male call pitch and female pitch preference between the two 13-year species was discovered. In this paper we report a strong association between calling song pitch and mtDNA haplotype for 101 individuals from a single locality within the M. tredecim/M. neotredecim contact zone and a strong association between abdomen colour and mtDNA haplotype. We conclude by reviewing proposed mechanisms for allochronic speciation and reproductive character displacement.

Sample preparation and storage can change arsenic speciation in human urine.

PubMed

Feldmann, J; Lai, V W; Cullen, W R; Ma, M; Lu, X; Le, X C

1999-11-01

Stability of chemical speciation during sample handling and storage is a prerequisite to obtaining reliable results of trace element speciation analysis. There is no comprehensive information on the stability of common arsenic species, such as inorganic arsenite [As(III)], arsenate [As(V)], monomethylarsonic acid, dimethylarsinic acid, and arsenobetaine, in human urine. We compared the effects of the following storage conditions on the stability of these arsenic species: temperature (25, 4, and -20 degrees C), storage time (1, 2, 4, and 8 months), and the use of additives (HCl, sodium azide, benzoic acid, benzyltrimethylammonium chloride, and cetylpyridinium chloride). HPLC with both inductively coupled plasma mass spectrometry and hydride generation atomic fluorescence detection techniques were used for the speciation of arsenic. We found that all five of the arsenic species were stable for up to 2 months when urine samples were stored at 4 and -20 degrees C without any additives. For longer period of storage (4 and 8 months), the stability of arsenic species was dependent on urine matrices. Whereas the arsenic speciation in some urine samples was stable for the entire 8 months at both 4 and -20 degrees C, other urine samples stored under identical conditions showed substantial changes in the concentration of As(III), As(V), monomethylarsonic acid, and dimethylarsinic acid. The use of additives did not improve the stability of arsenic speciation in urine. The addition of 0.1 mol/L HCl (final concentration) to urine samples produced relative changes in inorganic As(III) and As(V) concentrations. Low temperature (4 and -20 degrees C) conditions are suitable for the storage of urine samples for up to 2 months. Untreated samples maintain their concentration of arsenic species, and additives have no particular benefit. Strong acidification is not appropriate for speciation analysis.

The genomic landscape at a late stage of stickleback speciation: High genomic divergence interspersed by small localized regions of introgression.

PubMed

Ravinet, Mark; Yoshida, Kohta; Shigenobu, Shuji; Toyoda, Atsushi; Fujiyama, Asao; Kitano, Jun

2018-05-01

Speciation is a continuous process and analysis of species pairs at different stages of divergence provides insight into how it unfolds. Previous genomic studies on young species pairs have revealed peaks of divergence and heterogeneous genomic differentiation. Yet less known is how localised peaks of differentiation progress to genome-wide divergence during the later stages of speciation in the presence of persistent gene flow. Spanning the speciation continuum, stickleback species pairs are ideal for investigating how genomic divergence builds up during speciation. However, attention has largely focused on young postglacial species pairs, with little knowledge of the genomic signatures of divergence and introgression in older stickleback systems. The Japanese stickleback species pair, composed of the Pacific Ocean three-spined stickleback (Gasterosteus aculeatus) and the Japan Sea stickleback (G. nipponicus), which co-occur in the Japanese islands, is at a late stage of speciation. Divergence likely started well before the end of the last glacial period and crosses between Japan Sea females and Pacific Ocean males result in hybrid male sterility. Here we use coalescent analyses and Approximate Bayesian Computation to show that the two species split approximately 0.68-1 million years ago but that they have continued to exchange genes at a low rate throughout divergence. Population genomic data revealed that, despite gene flow, a high level of genomic differentiation is maintained across the majority of the genome. However, we identified multiple, small regions of introgression, occurring mainly in areas of low recombination rate. Our results demonstrate that a high level of genome-wide divergence can establish in the face of persistent introgression and that gene flow can be localized to small genomic regions at the later stages of speciation with gene flow.

Speciation distribution and mass balance of copper and zinc in urban rain, sediments, and road runoff.

PubMed

Zuo, Xiaojun; Fu, Dafang; Li, He

2012-11-01

Heavy metal pollution in road runoff had caused widespread concern since the last century. However, there are little references on metal speciation in multiple environmental media (e.g., rain, road sediments, and road runoff). Our research targeted the investigation of metal speciation in rain, road sediments, and runoff; the analysis of speciation variation and mass balance of metals among rain, road sediments, and runoff; the selection of main factors by principal component analysis (PCA); and the establishment of equation to evaluate the impact of rain and road sediments to metals in road runoff. Sequential extraction procedure contains five steps for the chemical fractionation of metals. Flame atomic absorption spectrometry (Shimadzu, AA-6800) was used to determine metal speciation concentration, as well as the total and dissolved fractions. The dissolved fractions for both Cu and Zn were dominant in rain. The speciation distribution of Zn was different from that of Cu in road sediments, while speciation distribution of Zn is similar to that of Cu in runoff. The bound to carbonates for both Cu and Zn in road sediments were prone to be dissolved by rain. The levels of Cu and Zn in runoff were not obviously influenced by rain, but significantly influenced by road sediments. The masses for both Cu and Zn among rain, road sediments, and road runoff approximately meet the mass balance equation for all rainfall patterns. Five principal factors were selected for metal regression equation based on PCA, including rainfall, average rainfall intensity, antecedent dry periods, total suspended particles, and temperature. The established regression equations could be used to predict the effect of road runoff on receiving environments.

Speciation of Reactive Sulfur Species and their Reactions with Alkylating Agents: Do we have any clue about what is present inside the cell?

PubMed

Bogdándi, Virág; Ida, Tomoaki; Sutton, Thomas R; Bianco, Christopher; Ditrói, Tamás; Koster, Grielof; Henthorn, Hillary A; Minnion, Magda; Toscano, John P; van der Vliet, Albert; Pluth, Michael D; Feelisch, Martin; Fukuto, Jon M; Akaike, Takaaki; Nagy, Péter

2018-06-17

Posttranslational modifications of cysteine (Cys) residues represent a major aspect of redox biology, and their reliable detection is key in providing mechanistic insights. The metastable character of these modifications and cell lysis-induced artifactual oxidation render current state-of-the-art protocols to rely on alkylation-based stabilization of labile Cys derivatives before cell/tissue rupture. An untested assumption in these procedures is that for all Cys derivatives alkylation rates are faster than their dynamic interchange. However, when the interconversion of Cys derivatives is not rate-limiting, then electrophilic labeling is under Curtin-Hammett control and hence the final alkylated mixture may not represent the speciation that prevailed before alkylation. We here present evidence that in the majority of cases, the speciation of alkylated polysulfide/thiol derivatives indeed depends on the experimental conditions. Our results reveal that alkylation perturbs sulfur speciation in both a concentration- and time-dependent manner, and that strong alkylating agents can cleave polysulfur chains. Moreover, we show that labeling of sulfenic acids with dimedone also affects Cys speciation, suggesting that part of the endogenous pool of products previously believed to represent sulfenic acid species may in fact represent polysulfides. These observations were obtained using buffered aqueous solutions of inorganic-, organic-, cysteine-, glutathione- and GAPDH-polysulfide species. Additional experiments in human plasma and serum revealed that monobromobimane can extract sulfide from the endogenous sulfur pool by shifting speciation equilibria, suggesting caution should be exercised when interpreting experimental results using this tool. We highlight methodological caveats potentially arising from these pitfalls and conclude that current derivatization strategies often fail to adequately capture physiologic speciation of sulfur species. This article is protected by copyright. All rights reserved.

Chemical Speciation and Metallomics.

PubMed

de Jesus, Jemmyson Romário; da Costa, Luana Ferreira; Lehmann, Eraldo Luiz; Galazzi, Rodrigo Moretto; Madrid, Katherine Chacón; Arruda, Marco Aurélio Zezzi

2018-01-01

Chemical speciation approaches is an inherent part of metallomics, once metals/metalloids and organic structures need to be currently evaluated for attaining metallomics studies. Then, this chapter focuses on the applications of the chemical speciation applied to the human health risk, food and human diet, drugs, forensic, nanoscience, and geological metallomics, also pointing out the advances in such area. Some aspects regarding sample preparation is commented along this chapter, and some strategies for maintaining the integrity of the metallomics information are also emphasized.

The phosphorus speciations in the sediments up- and down-stream of cascade dams along the middle Lancang River.

PubMed

Liu, Qi; Liu, Shiliang; Zhao, Haidi; Deng, Li; Wang, Cong; Zhao, Qinghe; Dong, Shikui

2015-02-01

We detected the longitudinal variability of phosphorus speciations and its relation to metals and grain size distribution of sediments in three cascade canyon reservoirs (Xiaowan, Manwan and Dachaoshan) along Lancang River, China. Five phosphorus speciations including loosely bound P (ex-P), reductant soluble P (BD-P), metal oxide-bound P (NaOH-P) calcium-bound P (HCl-P) and residual-P were extracted and quantified. Results showed that in Manwan Reservoir HCl-P accounted for the largest part of total phosphorus (TP) (49.69%), while in Xiaowan and Dachaoshan reservoirs, NaOH-P was the most abundant speciation which accounted for 57.21% and 55.19% of total phosphorus respectively. Higher contents of bio-available phosphorus in Xiaowan and Dachaoshan reservoirs suggested a high rate of P releasing from sediments. Results also showed ex-P and HCl-P had positive correlation with Ca. Total phosphorus was positively correlated with Fe. The silt/clay contents of the sediments had close relationship with ex-P (r=0.413, p<0.05), NaOH-P (r=0.428, p<0.05) and BAP (r=0.458, p<0.05). The concentration of Ca, Mn and silt/clay speciation in the sediments explained 40%, 10% and 4% of the spatial variation of phosphorus speciations, respectively. Copyright © 2014 Elsevier Ltd. All rights reserved.

Hybrid Speciation in a Marine Mammal: The Clymene Dolphin (Stenella clymene)

PubMed Central

Amaral, Ana R.; Lovewell, Gretchen; Coelho, Maria M.; Amato, George; Rosenbaum, Howard C.

2014-01-01

Natural hybridization may result in the exchange of genetic material between divergent lineages and even the formation of new taxa. Many of the Neo-Darwinian architects argued that, particularly for animal clades, natural hybridization was maladaptive. Recent evidence, however, has falsified this hypothesis, instead indicating that this process may lead to increased biodiversity through the formation of new species. Although such cases of hybrid speciation have been described in plants, fish and insects, they are considered exceptionally rare in mammals. Here we present evidence for a marine mammal, Stenella clymene, arising through natural hybridization. We found phylogenetic discordance between mitochondrial and nuclear markers, which, coupled with a pattern of transgressive segregation seen in the morphometric variation of some characters, support a case of hybrid speciation. S. clymene is currently genetically differentiated from its putative parental species, Stenella coerueloalba and Stenella longisrostris, although low levels of introgressive hybridization may be occurring. Although non-reticulate forms of evolution, such as incomplete lineage sorting, could explain our genetic results, we consider that the genetic and morphological evidence taken together argue more convincingly towards a case of hybrid speciation. We anticipate that our study will bring attention to this important aspect of reticulate evolution in non-model mammal species. The study of speciation through hybridization is an excellent opportunity to understand the mechanisms leading to speciation in the context of gene flow. PMID:24421898

Hybrid speciation in a marine mammal: the clymene dolphin (Stenella clymene).

PubMed

Amaral, Ana R; Lovewell, Gretchen; Coelho, Maria M; Amato, George; Rosenbaum, Howard C

2014-01-01

Natural hybridization may result in the exchange of genetic material between divergent lineages and even the formation of new taxa. Many of the Neo-Darwinian architects argued that, particularly for animal clades, natural hybridization was maladaptive. Recent evidence, however, has falsified this hypothesis, instead indicating that this process may lead to increased biodiversity through the formation of new species. Although such cases of hybrid speciation have been described in plants, fish and insects, they are considered exceptionally rare in mammals. Here we present evidence for a marine mammal, Stenella clymene, arising through natural hybridization. We found phylogenetic discordance between mitochondrial and nuclear markers, which, coupled with a pattern of transgressive segregation seen in the morphometric variation of some characters, support a case of hybrid speciation. S. clymene is currently genetically differentiated from its putative parental species, Stenella coerueloalba and Stenella longisrostris, although low levels of introgressive hybridization may be occurring. Although non-reticulate forms of evolution, such as incomplete lineage sorting, could explain our genetic results, we consider that the genetic and morphological evidence taken together argue more convincingly towards a case of hybrid speciation. We anticipate that our study will bring attention to this important aspect of reticulate evolution in non-model mammal species. The study of speciation through hybridization is an excellent opportunity to understand the mechanisms leading to speciation in the context of gene flow.

Ancient islands and modern invasions: disparate phylogeographic histories among Hispaniola's endemic birds.

PubMed

Sly, Nicholas D; Townsend, Andrea K; Rimmer, Christopher C; Townsend, Jason M; Latta, Steven C; Lovette, Irby J

2011-12-01

With its large size, complex topography and high number of avian endemics, Hispaniola appears to be a likely candidate for the in situ speciation of its avifauna, despite the worldwide rarity of avian speciation within single islands. We used multilocus comparative phylogeography techniques to examine the pattern and history of divergence in 11 endemic birds representing potential within-island speciation events. Haplotype and allele networks from mitochondrial ND2 and nuclear intron loci reveal a consistent pattern: phylogeographic divergence within or between closely related species is correlated with the likely distribution of ancient sea barriers that once divided Hispaniola into several smaller paleo-islands. Coalescent and mitochondrial clock dating of divergences indicate species-specific response to different geological events over the wide span of the island's history. We found no evidence that ecological or topographical complexity generated diversity, either by creating open niches or by restricting long-term gene flow. Thus, no true within-island speciation appears to have occurred among the species sampled on Hispaniola. Divergence events predating the merging of Hispaniola's paleo-island blocks cannot be considered in situ divergence, and postmerging divergence in response to episodic island segmentation by marine flooding probably represents in situ vicariance or interarchipelago speciation by dispersal. Our work highlights the necessity of considering island geologic history while investigating the speciation-area relationship in birds and other taxa. © 2011 Blackwell Publishing Ltd.

X exceptionalism in Caenorhabditis speciation.

PubMed

Cutter, Asher D

2017-11-13

Speciation genetics research in diverse organisms shows the X-chromosome to be exceptional in how it contributes to "rules" of speciation. Until recently, however, the nematode phylum has been nearly silent on this issue, despite the model organism Caenorhabditis elegans having touched most other topics in biology. Studies of speciation with Caenorhabditis accelerated with the recent discovery of species pairs showing partial interfertility. The resulting genetic analyses of reproductive isolation in nematodes demonstrate key roles for the X-chromosome in hybrid male sterility and inviability, opening up new understanding of the genetic causes of Haldane's rule, Darwin's corollary to Haldane's rule, and enabling tests of the large-X effect hypothesis. Studies to date implicate improper chromatin regulation of the X-chromosome by small RNA pathways as integral to hybrid male dysfunction. Sexual transitions in reproductive mode to self-fertilizing hermaphroditism inject distinctive molecular evolutionary features into the speciation process for some species. Caenorhabditis also provides unique opportunities for analysis in a system with XO sex determination that lacks a Y-chromosome, sex chromosome-dependent sperm competition differences and mechanisms of gametic isolation, exceptional accessibility to the development process and rapid experimental evolution. As genetic analysis of reproductive isolation matures with investigation of multiple pairs of Caenorhabditis species and new species discovery, nematodes will provide a powerful complement to more established study organisms for deciphering the genetic basis of and rules to speciation. © 2017 John Wiley & Sons Ltd.

Moran model as a dynamical process on networks and its implications for neutral speciation.

PubMed

de Aguiar, Marcus A M; Bar-Yam, Yaneer

2011-09-01

In population genetics, the Moran model describes the neutral evolution of a biallelic gene in a population of haploid individuals subjected to mutations. We show in this paper that this model can be mapped into an influence dynamical process on networks subjected to external influences. The panmictic case considered by Moran corresponds to fully connected networks and can be completely solved in terms of hypergeometric functions. Other types of networks correspond to structured populations, for which approximate solutions are also available. This approach to the classic Moran model leads to a relation between regular networks based on spatial grids and the mechanism of isolation by distance. We discuss the consequences of this connection for topopatric speciation and the theory of neutral speciation and biodiversity. We show that the effect of mutations in structured populations, where individuals can mate only with neighbors, is greatly enhanced with respect to the panmictic case. If mating is further constrained by genetic proximity between individuals, a balance of opposing tendencies takes place: increasing diversity promoted by enhanced effective mutations versus decreasing diversity promoted by similarity between mates. Resolution of large enough opposing tendencies occurs through speciation via pattern formation. We derive an explicit expression that indicates when speciation is possible involving the parameters characterizing the population. We also show that the time to speciation is greatly reduced in comparison with the panmictic case.

Moran model as a dynamical process on networks and its implications for neutral speciation

NASA Astrophysics Data System (ADS)

de Aguiar, Marcus A. M.; Bar-Yam, Yaneer

2011-03-01

In population genetics, the Moran model describes the neutral evolution of a biallelic gene in a population of haploid individuals subjected to mutations. We show in this paper that this model can be mapped into an influence dynamical process on networks subjected to external influences. The panmictic case considered by Moran corresponds to fully connected networks and can be completely solved in terms of hypergeometric functions. Other types of networks correspond to structured populations, for which approximate solutions are also available. This approach to the classic Moran model leads to a relation between regular networks based on spatial grids and the mechanism of isolation by distance. We discuss the consequences of this connection for topopatric speciation and the theory of neutral speciation and biodiversity. We show that the effect of mutations in structured populations, where individuals can mate only with neighbors, is greatly enhanced with respect to the panmictic case. If mating is further constrained by genetic proximity between individuals, a balance of opposing tendencies takes place: increasing diversity promoted by enhanced effective mutations versus decreasing diversity promoted by similarity between mates. Resolution of large enough opposing tendencies occurs through speciation via pattern formation. We derive an explicit expression that indicates when speciation is possible involving the parameters characterizing the population. We also show that the time to speciation is greatly reduced in comparison with the panmictic case.

Molecular evolutionary rates predict both extinction and speciation in temperate angiosperm lineages

PubMed Central

2010-01-01

Background A positive relationship between diversification (i.e., speciation) and nucleotide substitution rates is commonly reported for angiosperm clades. However, the underlying cause of this relationship is often unknown because multiple intrinsic and extrinsic factors can affect the relationship, and these have confounded previous attempts infer causation. Determining which factor drives this oft-reported correlation can lend insight into the macroevolutionary process. Results Using a new database of 13 time-calibrated angiosperm phylogenies based on internal transcribed spacer (ITS) sequences, and controlling for extrinsic variables of life history and habitat, I evaluated several potential intrinsic causes of this correlation. Speciation rates (λ) and relative extinction rates (ε) were positively correlated with mean substitution rates, but were uncorrelated with substitution rate heterogeneity. It is unlikely that the positive diversification-substitution correlation is due to accelerated molecular evolution during speciation (e.g., via enhanced selection or drift), because punctuated increases in ITS rate (i.e., greater mean and variation in ITS rate for rapidly speciating clades) were not observed. Instead, fast molecular evolution likely increases speciation rate (via increased mutational variation as a substrate for selection and reproductive isolation) but also increases extinction (via mutational genetic load). Conclusions In general, these results predict that clades with higher background substitution rates may undergo successful diversification under new conditions while clades with lower substitution rates may experience decreased extinction during environmental stasis. PMID:20515493

Selenium speciation in seleniferous agricultural soils under different cropping systems using sequential extraction and X-ray absorption spectroscopy.

PubMed

Qin, Hai-Bo; Zhu, Jian-Ming; Lin, Zhi-Qing; Xu, Wen-Po; Tan, De-Can; Zheng, Li-Rong; Takahashi, Yoshio

2017-06-01

Selenium (Se) speciation in soil is critically important for understanding the solubility, mobility, bioavailability, and toxicity of Se in the environment. In this study, Se fractionation and chemical speciation in agricultural soils from seleniferous areas were investigated using the elaborate sequential extraction and X-ray absorption near-edge structure (XANES) spectroscopy. The speciation results quantified by XANES technique generally agreed with those obtained by sequential extraction, and the combination of both approaches can reliably characterize Se speciation in soils. Results showed that dominant organic Se (56-81% of the total Se) and lesser Se(IV) (19-44%) were observed in seleniferous agricultural soils. A significant decrease in the proportion of organic Se to the total Se was found in different types of soil, i.e., paddy soil (81%) > uncultivated soil (69-73%) > upland soil (56-63%), while that of Se(IV) presented an inverse tendency. This suggests that Se speciation in agricultural soils can be significantly influenced by different cropping systems. Organic Se in seleniferous agricultural soils was probably derived from plant litter, which provides a significant insight for phytoremediation in Se-laden ecosystems and biofortification in Se-deficient areas. Furthermore, elevated organic Se in soils could result in higher Se accumulation in crops and further potential chronic Se toxicity to local residents in seleniferous areas. Copyright © 2017 Elsevier Ltd. All rights reserved.

In-line bulk supersaturation measurement by electrical conductometry in KDP crystal growth from aqueous solution

NASA Astrophysics Data System (ADS)

Bordui, P. F.; Loiacono, G. M.

1984-07-01

A method is presented for in-line bulk supersaturation measurement in crystal growth from aqueous solution. The method is based on a computer-controlled concentration measurement exploiting an experimentally predetermined cross-correlation between the concentration, electrical conductivity, and temperature of the growth solution. The method was applied to Holden crystallization of potassium dihydrogen phosphate (KDP). An extensive conductivity-temperature-concentration data base was generated for this system over a temperature range of 31 to 41°C. The method yielded continous, automated bulk supersaturation output accurate to within ±0.05 g KDP100 g water (±0.15% relative supersaturation).

The importance of ligand speciation in environmental research: a case study.

PubMed

Sillanpää, M; Orama, M; Rämö, J; Oikari, A

2001-02-21

The speciations of EDTA and DTPA in process, waste and river waters are modelled and simulated, specifically to the mode of occurrence in the pulp and paper mill effluents and subsequently in receiving waters. Due to relatively short residence times in bleaching process and waste water treatment and slow exchange kinetics, it is expected that the thermodynamic equilibrium is not necessarily reached. Therefore, the initial speciation plays a key role. As such, the simulations have been extended to the process waters of the pulp and paper industry taking into account estimated average conditions. The results reveal that the main species are; Mn and Ca complexes of EDTA and DTPA in pulp mill process waters; Fe(III) and Mn complexes of EDTA and DTPA in waste waters; Fe(III) and Zn complexes of EDTA and DTPA in receiving waters. It is also shown how the increasing concentration of complexing agents effects the speciation. Alkaline earth metal chelation plays a significant role in the speciation of EDTA and DTPA when there is a noticeable molar excess of complexing agents compared with transition metals.

Speciation through the lens of biomechanics: locomotion, prey capture and reproductive isolation.

PubMed

Higham, Timothy E; Rogers, Sean M; Langerhans, R Brian; Jamniczky, Heather A; Lauder, George V; Stewart, William J; Martin, Christopher H; Reznick, David N

2016-09-14

Speciation is a multifaceted process that involves numerous aspects of the biological sciences and occurs for multiple reasons. Ecology plays a major role, including both abiotic and biotic factors. Whether populations experience similar or divergent ecological environments, they often adapt to local conditions through divergence in biomechanical traits. We investigate the role of biomechanics in speciation using fish predator-prey interactions, a primary driver of fitness for both predators and prey. We highlight specific groups of fishes, or specific species, that have been particularly valuable for understanding these dynamic interactions and offer the best opportunities for future studies that link genetic architecture to biomechanics and reproductive isolation (RI). In addition to emphasizing the key biomechanical techniques that will be instrumental, we also propose that the movement towards linking biomechanics and speciation will include (i) establishing the genetic basis of biomechanical traits, (ii) testing whether similar and divergent selection lead to biomechanical divergence, and (iii) testing whether/how biomechanical traits affect RI. Future investigations that examine speciation through the lens of biomechanics will propel our understanding of this key process. © 2016 The Author(s).

250 years of hybridization between two biennial herb species without speciation.

PubMed

Matthews, Andrew; Emelianova, Katie; Hatimy, Abubakar A; Chester, Michael; Pellicer, Jaume; Ahmad, Khawaja Shafique; Guignard, Maité S; Rouhan, Germinal; Soltis, Douglas E; Soltis, Pamela S; Leitch, Ilia J; Leitch, Andrew R; Mavrodiev, Evgeny V; Buggs, Richard J A

2015-07-17

Hybridization between plant species can generate novel morphological diversity and lead to speciation at homoploid or polyploid levels. Hybrids between biennial herbs Tragopogon pratensis and T. porrifolius have been studied in experimental and natural populations for over 250 years. Here we examine their current status in natural populations in southeast England. All hybrids found were diploid; they tended to grow taller and with more buds than their parental species; many showed partial fertility; a few showed evidence of backcrossing. However, we found no evidence to suggest that the hybrids are establishing as a new species, nor can we find literature documenting speciation of these hybrids elsewhere. This lack of speciation despite at least 250 years of hybridization contrasts with the fact that both parental species have formed new allopolyploid species through hybridization with another diploid, T. dubius. Understanding why hybrids often do not speciate, despite repeated opportunities, would enhance our understanding of both the evolutionary process and risk assessments of invasive species. Published by Oxford University Press on behalf of the Annals of Botany Company.

Complete genomes of Hairstreak butterflies, their speciation, and nucleo-mitochondrial incongruence

PubMed Central

Cong, Qian; Shen, Jinhui; Borek, Dominika; Robbins, Robert K.; Otwinowski, Zbyszek; Grishin, Nick V.

2016-01-01

Comparison of complete genomes of closely related species enables research on speciation and how phenotype is determined by genotype. Lepidoptera, an insect order of 150,000 species with diverse phenotypes, is well-suited for such comparative genomics studies if new genomes, which cover additional Lepidoptera families are acquired. We report a 729 Mbp genome assembly of the Calycopis cecrops, the first genome from the family Lycaenidae and the largest available Lepidoptera genome. As detritivore, Calycopis shows expansion in detoxification and digestion enzymes. We further obtained complete genomes of 8 Calycopis specimens: 3 C. cecrops and 5 C. isobeon, including a dry specimen stored in the museum for 30 years. The two species differ subtly in phenotype and cannot be differentiated by mitochondrial DNA. However, nuclear genomes revealed a deep split between them. Genes that can clearly separate the two species (speciation hotspots) mostly pertain to circadian clock, mating behavior, transcription regulation, development and cytoskeleton. The speciation hotspots and their function significantly overlap with those we previously found in Pterourus, suggesting common speciation mechanisms in these butterflies. PMID:27120974

Transformation of heavy metal speciation during sludge drying: mechanistic insights.

PubMed

Weng, Huan-Xin; Ma, Xue-Wen; Fu, Feng-Xia; Zhang, Jin-Jun; Liu, Zan; Tian, Li-Xun; Liu, Chongxuan

2014-01-30

Speciation can fundamentally affect on the stability and toxicity of heavy metals in sludge from wastewater treatment plants. This research investigated the speciation of heavy metals in sludge from both municipal and industrial sources, and metal speciation change as a result of drying process to reduce sludge volume. The changes in sludge properties including sludge moisture content, temperature, density, and electrical conductivity were also monitored to provide insights into the mechanisms causing the change in heavy metal speciation. The results show that the drying process generally stabilized Cr, Cu, Cd, and Pb in sludge by transforming acid-soluble, reducible, and oxidizable species into structurally stable forms. Such transformation and stabilization occurred regardless of the sludge source and type, and were primarily caused by the changes in sludge properties associated with decomposition of organic matter and sulfide. The results enhanced our understanding of the geochemical behavior of heavy metals in municipal sludge, and are useful for designing a treatment system for environment-friendly disposal of sludge. Copyright © 2013 Elsevier B.V. All rights reserved.

A review of recent developments in the speciation and location of arsenic and selenium in rice grain

PubMed Central

Carey, Anne-Marie; Lombi, Enzo; Donner, Erica; de Jonge, Martin D.; Punshon, Tracy; Jackson, Brian P.; Guerinot, Mary Lou; Price, Adam H.; Meharg, Andrew A.

2014-01-01

Rice is a staple food yet is a significant dietary source of inorganic arsenic, a class 1, nonthreshold carcinogen. Establishing the location and speciation of arsenic within the edible rice grain is essential for understanding the risk and for developing effective strategies to reduce grain arsenic concentrations. Conversely, selenium is an essential micronutrient and up to 1 billion people worldwide are selenium-deficient. Several studies have suggested that selenium supplementation can reduce the risk of some cancers, generating substantial interest in biofortifying rice. Knowledge of selenium location and speciation is important, because the anti-cancer effects of selenium depend on its speciation. Germanic acid is an arsenite/silicic acid analogue, and location of germanium may help elucidate the mechanisms of arsenite transport into grain. This review summarises recent discoveries in the location and speciation of arsenic, germanium, and selenium in rice grain using state-of-the-art mass spectrometry and synchrotron techniques, and illustrates both the importance of high-sensitivity and high-resolution techniques and the advantages of combining techniques in an integrated quantitative and spatial approach. PMID:22159463

Complete genomes of Hairstreak butterflies, their speciation, and nucleo-mitochondrial incongruence.

PubMed

Cong, Qian; Shen, Jinhui; Borek, Dominika; Robbins, Robert K; Otwinowski, Zbyszek; Grishin, Nick V

2016-04-28

Comparison of complete genomes of closely related species enables research on speciation and how phenotype is determined by genotype. Lepidoptera, an insect order of 150,000 species with diverse phenotypes, is well-suited for such comparative genomics studies if new genomes, which cover additional Lepidoptera families are acquired. We report a 729 Mbp genome assembly of the Calycopis cecrops, the first genome from the family Lycaenidae and the largest available Lepidoptera genome. As detritivore, Calycopis shows expansion in detoxification and digestion enzymes. We further obtained complete genomes of 8 Calycopis specimens: 3 C. cecrops and 5 C. isobeon, including a dry specimen stored in the museum for 30 years. The two species differ subtly in phenotype and cannot be differentiated by mitochondrial DNA. However, nuclear genomes revealed a deep split between them. Genes that can clearly separate the two species (speciation hotspots) mostly pertain to circadian clock, mating behavior, transcription regulation, development and cytoskeleton. The speciation hotspots and their function significantly overlap with those we previously found in Pterourus, suggesting common speciation mechanisms in these butterflies.

Speciation through the lens of biomechanics: locomotion, prey capture and reproductive isolation

PubMed Central

Rogers, Sean M.; Langerhans, R. Brian; Jamniczky, Heather A.; Lauder, George V.; Stewart, William J.; Martin, Christopher H.; Reznick, David N.

2016-01-01

Speciation is a multifaceted process that involves numerous aspects of the biological sciences and occurs for multiple reasons. Ecology plays a major role, including both abiotic and biotic factors. Whether populations experience similar or divergent ecological environments, they often adapt to local conditions through divergence in biomechanical traits. We investigate the role of biomechanics in speciation using fish predator–prey interactions, a primary driver of fitness for both predators and prey. We highlight specific groups of fishes, or specific species, that have been particularly valuable for understanding these dynamic interactions and offer the best opportunities for future studies that link genetic architecture to biomechanics and reproductive isolation (RI). In addition to emphasizing the key biomechanical techniques that will be instrumental, we also propose that the movement towards linking biomechanics and speciation will include (i) establishing the genetic basis of biomechanical traits, (ii) testing whether similar and divergent selection lead to biomechanical divergence, and (iii) testing whether/how biomechanical traits affect RI. Future investigations that examine speciation through the lens of biomechanics will propel our understanding of this key process. PMID:27629033

Selective hydride generation- cryotrapping- ICP-MS for arsenic speciation analysis at picogram levels: analysis of river and sea water reference materials and human bladder epithelial cells

PubMed Central

Matoušek, Tomáš; Currier, Jenna M.; Trojánková, Nikola; Saunders, R. Jesse; Ishida, María C.; González-Horta, Carmen; Musil, Stanislav; Mester, Zoltán; Stýblo, Miroslav; Dědina, Jiří

2013-01-01

An ultra sensitive method for arsenic (As) speciation analysis based on selective hydride generation (HG) with preconcentration by cryotrapping (CT) and inductively coupled plasma- mass spectrometry (ICP-MS) detection is presented. Determination of valence of the As species is performed by selective HG without prereduction (trivalent species only) or with L-cysteine prereduction (sum of tri- and pentavalent species). Methylated species are resolved on the basis of thermal desorption of formed methyl substituted arsines after collection at −196°C. Limits of detection of 3.4, 0.04, 0.14 and 0.10 pg mL−1 (ppt) were achieved for inorganic As, mono-, di- and trimethylated species, respectively, from a 500 μL sample. Speciation analysis of river water (NRC SLRS-4 and SLRS-5) and sea water (NRC CASS-4, CASS-5 and NASS-5) reference materials certified to contain 0.4 to 1.3 ng mL−1 total As was performed. The concentrations of methylated As species in tens of pg mL−1 range obtained by HG-CT-ICP-MS systems in three laboratories were in excellent agreement and compared well with results of HG-CT-atomic absorption spectrometry and anion exchange liquid chromatography- ICP-MS; sums of detected species agreed well with the certified total As content. HG-CT-ICP-MS method was successfully used for analysis of microsamples of exfoliated bladder epithelial cells isolated from human urine. Here, samples of lysates of 25 to 550 thousand cells contained typically tens pg up to ng of iAs species and from single to hundreds pg of methylated species, well within detection power of the presented method. A significant portion of As in the cells was found in the form of the highly toxic trivalent species. PMID:24014931

Magnetic solid phase extraction coupled with inductively coupled plasma mass spectrometry for the speciation of mercury in environmental water and human hair samples.

PubMed

Ma, Shishuai; He, Man; Chen, Beibei; Deng, Wenchao; Zheng, Qi; Hu, Bin

2016-01-01

In this work, γ-mercaptopropyltrimethoxysilane (γ-MPTS) modified Fe3O4@SiO2 magnetic nanoparticles (MNPs) was successfully prepared, and characterized by Fourier transform infrared spectrometer (FT-IR), Transmission electron microscope (TEM) and Vibrating sample magnetometer (VSM). The sorption performance of the prepared Fe3O4@SiO2@γ-MPTS MNPs towards methylmercury (CH3Hg(+)) and inorganic mercury (Hg(2+)) was investigated. It was found that CH3Hg(+) and Hg(2+) could be simultaneously retained on the prepared Fe3O4@SiO2@γ-MPTS MNPs, and the quantitative elution of CH3Hg(+) and total mercury (THg) was achieved by using 1.5 mol L(-1) HCl containing 0.01% and 3% thiourea (m/v), respectively. And the levels of Hg(2+) were obtained by subtracting CH3Hg(+) from THg. Based on the above facts, a method of magnetic solid phase extraction (MSPE) combined with inductively coupled plasma mass spectrometry (ICP-MS) was developed for the speciation of CH3Hg(+) and Hg(2+). Various experimental parameters affecting MSPE of CH3Hg(+) and Hg(2+) such as pH, eluent, sample volume, and co-existing ions have been studied. Under the optimized conditions, the limits of detection (LODs) for CH3Hg(+) and THg were 1.6 and 1.9 ng L(-1), respectively. The accuracy of the proposed method was validated by analysis of a Certified Reference Material NRCC DORM-2 dogfish muscle, and the determined values are in good agreement with the certified values. The proposed method has also been successfully applied for the speciation of CH3Hg(+) and Hg(2+) in environmental water and human hair samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Resolving colocalization of bacteria and metal(loid)s on plant root surfaces by combining fluorescence in situ hybridization (FISH) with multiple-energy micro-focused X-ray fluorescence (ME μXRF).

PubMed

Honeker, Linnea K; Root, Robert A; Chorover, Jon; Maier, Raina M

2016-12-01

Metal(loid)-contamination of the environment due to anthropogenic activities is a global problem. Understanding the fate of contaminants requires elucidation of biotic and abiotic factors that influence metal(loid) speciation from molecular to field scales. Improved methods are needed to assess micro-scale processes, such as those occurring at biogeochemical interfaces between plant tissues, microbial cells, and metal(loid)s. Here we present an advanced method that combines fluorescence in situ hybridization (FISH) with synchrotron-based multiple-energy micro-focused X-ray fluorescence microprobe imaging (ME μXRF) to examine colocalization of bacteria and metal(loid)s on root surfaces of plants used to phytostabilize metalliferous mine tailings. Bacteria were visualized on a small root section using SytoBC nucleic acid stain and FISH probes targeting the domain Bacteria and a specific group (Alphaproteobacteria, Gammaproteobacteria, or Actinobacteria). The same root region was then analyzed for elemental distribution and metal(loid) speciation of As and Fe using ME μXRF. The FISH and ME μXRF images were aligned using ImageJ software to correlate microbiological and geochemical results. Results from quantitative analysis of colocalization show a significantly higher fraction of As colocalized with Fe-oxide plaques on the root surfaces (fraction of overlap 0.49±0.19) than to bacteria (0.072±0.052) (p<0.05). Of the bacteria that colocalized with metal(loid)s, Actinobacteria, known for their metal tolerance, had a higher correlation with both As and Fe than Alphaproteobacteria or Gammaproteobacteria. This method demonstrates how coupling these micro-techniques can expand our understanding of micro-scale interactions between roots, metal(loid)s and microbes, information that should lead to improved mechanistic models of metal(loid) speciation and fate. Copyright © 2016 Elsevier B.V. All rights reserved.

Anaerobic Digestion Alters Copper and Zinc Speciation.

PubMed

Legros, Samuel; Levard, Clément; Marcato-Romain, Claire-Emmanuelle; Guiresse, Maritxu; Doelsch, Emmanuel

2017-09-19

Anaerobic digestion is a widely used organic waste treatment process. However, little is known on how it could alter the speciation of contaminants in organic waste. This study was focused on determining the influence of anaerobic digestion on the speciation of copper and zinc, two metals that generally occur at high concentration in organic waste. Copper and zinc speciation was investigated by X-ray absorption spectroscopy in four different raw organic wastes (predigestion) and their digested counterparts (postdigestion, i.e., digestates). The results highlighted an increase in the digestates of the proportion of amorphous or nanostructured copper sulfides as well as amorphous or nanostructured zinc sulfides and zinc phosphate as compared to raw waste. We therefore suggest that the environmental fate of these elements would be different when spreading either digestates or raw waste on cropland.

Bulk superhard B-C-N nanocomposite compact and method for preparing thereof

DOEpatents

Zhao, Yusheng; He, Duanwei

2004-07-06

Bulk, superhard, B-C-N nanocomposite compact and method for preparing thereof. The bulk, superhard, nanocomposite compact is a well-sintered compact and includes nanocrystalline grains of at least one high-pressure phase of B-C-N surrounded by amorphous diamond-like carbon grain boundaries. The bulk compact has a Vicker's hardness of about 41-68 GPa. It is prepared by ball milling a mixture of graphite and hexagonal boron nitride, encapsulating the ball-milled mixture, and sintering the encapsulated ball-milled mixture at a pressure of about 5-25 GPa and at a temperature of about 1000-2500 K.

Factors affecting the toxicity of trace metals to fertilization success in broadcast spawning marine invertebrates: A review.

PubMed

Hudspith, M; Reichelt-Brushett, Amanda; Harrison, Peter L

2017-03-01

Significant amounts of trace metals have been released into both nearshore and deep sea environments in recent years, resulting in increased concentrations that can be toxic to marine organisms. Trace metals can negatively affect external fertilization processes in marine broadcast spawners and may cause a reduction in fertilization success at elevated concentrations. Due to its sensitivity and ecological importance, fertilization success has been widely used as a toxicity endpoint in ecotoxicological testing, which is an important method of evaluating the toxicity of contaminants for management planning. Ecotoxicological data regarding fertilization success are available across the major marine phyla, but there remain uncertainties that impair our ability to confidently interpret and analyse these data. At present, the cellular and biochemical events underlying trace metal toxicity in external fertilization are not known. Metal behavior and speciation play an important role in bioavailability and toxicity but are often overlooked, and disparities in experimental designs between studies limit the degree to which results can be synthesised and compared to those of other relevant species. We reviewed all available literature covering cellular toxicity mechanisms, metal toxicities and speciation, and differences in methodologies between studies. We conclude that the concept of metal toxicity should be approached in a more holistic manner that involves elucidating toxicity mechanisms, improving the understanding of metal behavior and speciation on bioavailability and toxicity, and standardizing the fertilization assay methods among different groups of organisms. We identify opportunities to improve the fertilization assay that will allow robust critical and comparative analysis between species and their sensitivities to trace metals during external fertilization, and enable data to be more readily extrapolated to field conditions. Copyright © 2017 Elsevier B.V. All rights reserved.

Sequential photocatalyst-assisted digestion and vapor generation device coupled with anion exchange chromatography and inductively coupled plasma mass spectrometry for speciation analysis of selenium species in biological samples.

PubMed

Tsai, Yun-ni; Lin, Cheng-hsing; Hsu, I-hsiang; Sun, Yuh-chang

2014-01-02

We have developed an on-line sequential photocatalyst-assisted digestion and vaporization device (SPADVD), which operates through the nano-TiO2-catalyzed photo-oxidation and reduction of selenium (Se) species, for coupling between anion exchange chromatography (LC) and inductively coupled plasma mass spectrometry (ICP-MS) systems to provide a simple and sensitive hyphenated method for the speciation analysis of Se species without the need for conventional chemical digestion and vaporization techniques. Because our proposed on-line SPADVD allows both organic and inorganic Se species in the column effluent to be converted on-line into volatile Se products, which are then measured directly through ICP-MS, the complexity of the procedure and the probability of contamination arising from the use of additional chemicals are both low. Under the optimized conditions for SPADVD - using 1g of nano-TiO2 per liter, at pH 3, and illuminating for 80 s - we found that Se(IV), Se(VI), and selenomethionine (SeMet) were all converted quantitatively into volatile Se products. In addition, because the digestion and vaporization efficiencies of all the tested selenicals were improved when using our proposed on-line LC/SPADVD/ICP-MS system, the detection limits for Se(IV), Se(VI), and SeMet were all in the nanogram-per-liter range (based on 3σ). A series of validation experiments - analysis of neat and spiked extracted samples - indicated that our proposed methods could be applied satisfactorily to the speciation analysis of organic and inorganic Se species in the extracts of Se-enriched supplements. Copyright © 2013. Published by Elsevier B.V.

On-line preconcentration and speciation of arsenic by flow injection hydride generation atomic absorption spectrophotometry.

PubMed

Narcise, Cristine Ingrid S; Coo, Lilibeth Dlc; Del Mundo, Florian R

2005-12-15

A flow injection-column preconcentration-hydride generation atomic absorption spectrophotometric (FI-column-HGAAS) method was developed for determining mug/l levels of As(III) and As(V) in water samples, with simultaneous preconcentration and speciation. The speciation scheme involved determining As(V) at neutral pH and As(III+V) at pH 12, with As(III) obtained by difference. The enrichment factor (EF) increased with increase in sample loading volume from 2.5 to 10ml, and for preconcentration using the chloride-form anion exchange column, EFs ranged from 5 to 48 for As(V) and 4 to 24 for As(III+V), with corresponding detection limits of 0.03-0.3 and 0.07-0.3mug/l. Linear concentration range (LCR) also varied with sample loading volume, and for a 5-ml sample was 0.3-5 and 0.2-8mug/l for As(V) and As(III+V), respectively. Sample throughput, which decreased with increase in sample volume, was 8-17 samples/h. For the hydroxide-form column, the EFS for 2.5-10ml samples were 3-23 for As(V) and 2-15 for As(III+V), with corresponding detection limits of 0.07-0.4 and 0.1-0.5mug/l. The LCR for a 5-ml sample was 0.3-10mug/l for As(V) and 0.2-20mug/l for As(III+V). Sample throughput was 10-20 samples/h. The developed method has been effectively applied to tap water and mineral water samples, with recoveries ranging from 90 to 102% for 5-ml samples passed through the two columns.